Complete dechlorination of endosulfan and lindane using Mg0/Pd(+4) bimetallic system

A Mg0/Pd(+4) bimetallic system was evaluated to dechlorinate endosulfan and lindane in the aqueous phase. Studies were conducted with endosulfan and lindane separately, with or without acid in a 1:1 (v/v) water:acetone phase. In the absence of any acid, higher degradation of endosulfan and lindane was observed using Mg0/Pd(+4) doses of 10/0.5 and 4/0.1 mg/mL, respectively. Acetone plays an important role in facilitating the dechlorination reaction by increasing the solubilities of pesticides. Dechlorination kinetics for endosulfan and lindane (30 and 50 mg/L [30 and 50 ppm] concentration of each pesticide) were conducted with varying Mg0/Pd(+4) doses, and the time-course profiles were well-fitted into exponential curves. The optimum observed rate constants (k(obs)) for endosulfan and lindane were obtained with Mg0/Pd(+4) doses of 5/0.5 and 4/0.1 mg/mL, respectively. Gas chromatography-mass spectrometry analyses revealed that endosulfan and lindane were dechlorinated completely into their hydrocarbon skeletons-Bicyclo [2,2,1] hepta 2-5 diene and benzene, respectively.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用,给人类带来了较大危害.为此,采用纳米铁粉这一新方法对其进行脱氯处理.试验以纳米级铁粉对四氯化碳的脱氯率为考察指标,选用L25(56)正交试验方案,考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素.结果表明,pH值这一因素有极显著影响;在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下,获得了99.5%的脱氯率,为有机氯化物脱氯开辟了一条新途径.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用，给人类带来了较大危害。为此，采用纳米铁粉这一新方法对其进行脱氯处理。试验以纳米级铁粉对四氯化碳的脱氯率为考察指标，选用L25（5^6）正交试验方案，考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素。结果表明，pH值这一因素有极显著影响；在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下，获得了99．5％的脱氯率，为有机氯化物脱氯开辟了一条新途径。     

Effects of temperature and dissolved oxygen on Se(IV) removal and Se(0) precipitation by Shewanella sp. HN-41

Facultative anaerobic Shewanella sp. strain HN-41 was able to utilize selenite (Se(IV)) as a sole electron acceptor for respiration in anaerobic condition, resulting in reduction of Se(IV) and then precipitation of elemental Se nano-sized spherical particles, which were identified using energy-dispersive X-ray spectroscopy and X-ray absorption near-edge structure spectroscopy. When the effects on Se(IV) reduction to elemental Se were studied by varying incubation temperatures and dissolved oxygen contents, Se(IV) reduction occurred more actively with higher removal rate of Se(IV) in aqueous phase and well-shaped spherical Se(0) nanoparticles were formed from the incubations under N(2) (100%) or N(2):O(2) (80%:20%) at 30 degrees C with average diameter values of 181+/-40 nm and 164+/-24 nm, respectively, while relatively less amounts of irregular-shaped Se(0) nanoparticles were produced with negligible amount of Se(IV) reduction and removal under 100% of O(2). The Se particle size distributions based on scanning electron microscopy also showed a general tendency towards decreased Se particle size as oxygen content increased, whereas the particle size seemed uncorrelated to the change in the incubation temperature. These results also suggest that the size-controlled biological Se(0) nanospheres production may be achieved simply by changing the culture conditions.     

Linear free energy relationships for dechlorination of aromatic chlorides by Pd/Fe

Reductive dechlorination rate constants for five chlorobenzenes in the presence of Pd/Fe as catalyst were determined experimentally. Linear free energy relationships (LFER) for the dechlorination rate constants of five chlorobenzenes and three chlorophenols were developed by partial least squares (PLS) regression based on quantum chemical parameters computed by PM3 Hamiltonian. The optimal LFER model obtained is

logk=−1.63+1.46×10⁻³ΔH_f−7.69×10⁻¹E_LUMO

where k stands for the dechlorination rate constants, ΔH_f is the standard heat of formation, and E_LUMO is the energy of the lowest unoccupied molecular orbital. The Q²_cum value of the model is 0.879, indicating good robustness and predictive power of the model.     

The complete dechlorination of DDT by magnesium/palladium bimetallic particles

The complete dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) by a magnesium/palladium bimetallic system has been accomplished. The reaction takes place under ambient temperature and pressure and mild reaction conditions requiring only 0.25 g of magnesium and 0.3% palladium (wt/wt) to drive the dechlorination of 100 microg DDT (50 ppm in 2 ml). The process is both rapid and complete requiring less than 10 min to attain total dechlorination within the detection limit (approximately 10 pg for DDT) of electron capture detection gas chromatography (GC-ECD). The major product formed, as deduced from mass spectrometry (GC-MS) is the hydrocarbon skeleton, 1,1-diphenylethane. This technology may allow for the development of an economic and environmentally benign method of DDT remediation.     

Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe(zero-valent) particles supported on chitosan and silica

In this study, nanoscale Pd-Fe particles, with diameters less than 100 nm, were synthesized and dispersed over the chitosan and silica supports. Three different Pd-Fe particles were synthesized, namely 0.1% Pd-Fe, 0.5% Pd-Fe and 1.0% Pd-Fe. SEM images confirmed that the Pd-Fe particles were dispersed over the surface of the supports while SEM-EDX confirmed evenly distribution of Pd over Fe(zero-valent). alpha-Fe(zero-valent) crystallites were identified by means of XRD and observed in TEM. Reductive dechlorinations of 1,2,4-trichlorobenzene (1,2,4-TCB) with the nanoscale Pd-Fe/chitosan and Pd-Fe/silica were carried out in the batch experiment system. Disappearance of the parent species and formation of the reaction intermediates and end product were monitored at discrete times. The results show that the nano-scale Pd-Fe particles were able to completely dechlorinate the chlorinated benzenes within a very short timescale. Complete dechlorinations of 1,2,4-TCB to benzene were achieved within 60 min with the 1.0% Pd-Fe/chitosan and within 100 min with the 1.0% Pd-Fe/silica. Reaction rates were observed to increase with increasing Pd content of the Pd-Fe/support. The reactions apparently followed pseudo-first-order kinetics with respect to the 1,2,4-TCB transformation. A kinetic model is constructed to fit the experimental results for the reactions, enabling identification of the major and minor dechlorination pathways of 1,2,4-TCB. The model suggests that the 1,2,4-TCB transformation mainly followed the primary pathway of direct reductive dechlorination to benzene and secondary pathway of sequential hydrogenolysis to 1,2-dichlorobenzene (1,2-DCB) and then chlorobenzene (CB) or benzene.     

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

Reductive dechlorination of chlorinated methanes and ethanes by reduced iron (II) porphyrins

The reaction of a reduced iron (II) porphyrin with a series of chlorinated methanes and ethanes was examined under neutral conditions in buffered aqueous solutions containing an excess of the reducing agent. Carbon tetrachloride, chloroform and 1,1,1-trichloroethane were reduced to lower chlorinated homologs, while methylene chloride, 1,1,2-trichloroethane and 1,1-dichloroethane did not appear to be degraded in this system.     

Effects of anions on the kinetics and reactivity of nanoscale Pd/Fe in trichlorobenzene dechlorination

Influences of anionic co-solutes on dechlorination of 1,2,4-trichlorobenzene (124TCB) by the nanoscale Pd/Fe particles were investigated in batch experiments in the presence of an anionic solute such as nitrate, nitrite, perchlorate, phosphate, carbonate, silica, sulfate, sulfite, or sulfide. Based on the extent of inhibitory effects on the 124TCB dechlorination, the anions can be ranked in the order of: control≈sulfate≈silica相似文献   

Effect of metal and glycol on mechanochemical dechlorination of polychlorinated biphenyls (PCBs)

This paper assesses the potential of mechanochemical method with fine metal powder, glycol and alkali for polychlorinated biphenyls (PCBs) removal from waste insulating oil. The effects of relevant parameters, such as kinds of chemicals, rate and time of milling were examined. After each run, the total PCBs content in waste insulating oil was measured. Polyethylene glycol 200, long chain-glycol was more effective than triethylene glycol and ethylene glycol, short chain-glycol as hydrogen donor in mechanochemical dechlorination of PCBs. A maximum of 99.9% PCBs removal (below 2ppm) and 94% total chlorine removal were achieved with the mechanochemical process for 2h.     

Batch reactor kinetic studies on the reductive dechlorination of chlorinated ethylenes by tetrakis-(4-sulfonatophenyl)porphyrin cobalt

Tetrakis-(4-sulfonatophenyl)porphyrin cobalt was identified as a highly-active reductive dechlorination catalyst for chlorinated ethylenes. Through batch reactor kinetic studies, degradation of chlorinated ethylenes proceeded in a step-wise fashion with the sequential replacement of Cl by H. For perchloroethylene (PCE) and trichloroethylene (TCE), the dechlorination products were quantified and the C₂ mass was accounted for. Degradation of the chlorinated ethylenes was found to be first-order in substrate. Dechlorination trials with increasing catalyst concentration showed a linearly increasing pseudo first-order rate constant which yielded rate laws for PCE and TCE degradation that are first-order in catalyst. The dechlorination activity of this catalyst was compared to that of another water-soluble cobalt porphyrin under the same reaction conditions and found to be comparable for PCE and TCE.     

The study on the dechlorination of OCDD with Pd/C catalyst in ethanol-water solution under mild conditions

Dechlorination of octachlorodibenzo-p-dioxin (OCDD) was carried out in ethanol-water (v/v=1:1) solution of NaOH in the presence of Pd/C catalysts with the use of H(2). The substrate was dechlorinated with Pd/C under mild conditions (atmospheric pressure and <100 degrees C) to give a chlorine-free product, dibenzo-p-dioxin (DD), in high yields. After reaction of 3h at 50 degrees C, 95.9% OCDD was degraded to low dechlorinated congeners and the yield of DD was 77.4%. We have also studied the dechlorination selectivity of chlorine atoms on the different substituted positions and postulated the dechlorination pathway of OCDD. For OCDD, the 2-position has higher reactivity than 1-position, but the difference is very small. From the distribution statistics of the intermediates during the reaction, we postulate that the steric effect plays an important role during the reaction and affect the dechlorination pathway of OCDD.     

微波活化对Ca(OH)2孔隙结构及脱氯性能的影响

采用微波炉对一定质量的氢氧化钙样品进行活化,利用压汞仪考察了不同微波活化时间及脱氯反应前后的Ca(OH)2总比孔表面积、分段比表面积和孔径分布的变化,并在脱氯实验台上对脱氯效率进行实际测试。结果表明,微波活化存在一个最佳时间,在此时间内样品比孔表面积增大50%左右,而超过这一时间样品比表面积回复性减小;微波活化主要通过增加3～20 nm孔径段的微孔为样品提供更大比表面积;这些新增加的微孔在脱氯反应过程中被完全利用或消耗; 最佳活化时间下的微波活化使Ca(OH)2在较低Ca/Cl摩尔比下获得更大脱氯效率,Ca/Cl摩尔比=4.1时,脱氯效率增加了20%。     

Synergic effect of calcium oxide and iron (III) oxide on the dechlorination of hexachlorobenzene

Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.     

Electrochemical dechlorination of chloroacetic acids (CAAs) using hemoglobin-loaded carbon nanotube electrode

Hemoglobin (Hb) was immobilized on carbon nanotube (CNT) electrode to catalyze the dechlorination of chloroacetic acids (CAAs), and the electrocatalytic behaviors of the Hb-loaded electrode for the dechlorination of trichloroacetic acid (TCAA) were studied by cyclic voltammetry and constant-potential electrolysis technique. An Hb-loaded packed-bed flow reactor was also constructed for bioelectrocatalytic dechloriantion of CAAs from drinking water. The results showed that the reduced heme of Hb immobilized on CNT electrode was easily regenerated, and Hb exhibited a stable and high activity for reductive dechlorination of CAAs with significant lowering of overpotential. TCAA could be reduced at -0.450 V (vs. saturated calomel electrode (SCE)) with catalysis of Hb-loaded electrode and its dechlorination was stepwise, following the pathway of TCAA-->dichloroacetic acid (DCAA)-->monochloroacetic acid (MCAA)-->acetic acid. It was also found that all CAAs, e.g., TCAA, DCAA and MCAA, could be dechlorinated completely at -0.450 V. The removal of 30.0 mM TCAA and DCAA is ca. 40% and 31%, respectively, with electrolysis for 100 min at -0.600 V (vs. SCE) using the Hb-loaded packed-bed flow reactor. The dechlorination activities of CAAs follow the decreasing order: TCAA>DCAA>MCAA, and the average current efficiency is over 90%.     

Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II)

Degradative solidification/stabilization (DS/S) is a novel remediation technology that combines chemical degradation with conventional solidification/stabilization. The applicability of the Fe(II)-based DS/S to treating chlorinated alkanes was tested by characterizing degradation reactions of carbon tetrachloride (CT) and its daughter products in cement slurries containing Fe(II). Degradation kinetics of CT and chloroform (CF) were generally very rapid with reaction rates comparable to rates that can be obtained with zero-valent iron. Dechlorination reactions of CT proceeded primarily via a hydrogenolysis pathway, which yielded CF and methylene chloride (MC) as major products and chloromethane and methane as minor products. However, reaction pathways other than hydrogenolysis also appeared to be important at very high pH conditions. MC apparently was resistant to dechlorination reactions over a period of about two months. Kinetics of CT and CF transformation were strongly dependent on pH with an optimal value around 13, which was higher than found previously for PCE. When the initial CF concentration varied between 0.01 and 1 mM, and the Fe(II) dose was 104 mM, pseudo-first-order kinetics generally described the degradation reactions of CF. However, there was also some indication of substrate saturation kinetics in these experiments. This suggests that a saturation model would better describe the kinetics in systems with higher concentration of substrates or lower concentration of the reactive surfaces.     

Kinetics of chromium (VI) reduction by a type strain Shewanella alga under different growth conditions.

We conducted kinetic batch experiments to determine the reduction of Chromium(VI) by a type strain of Shewanella alga (BrY-MT) ATCC 55627. Chromium(VI) was reduced to Chromium(III) by BrY-MT grown in three different substrates: BHIB (brain heart infusion broth), TSB (tryptic soy broth), and M9 (minimum broth). Four different Cr(VI) concentrations 4.836, 10.00, 37.125, and 260.00 mg l-1 were reduced at different rates by BrY-MT in both aerobic and anaerobic conditions. BrY-MT grown in BHIB reduced the maximum amount of Cr(VI) followed by TSB and M9. Carbondioxide produced from bacterial respiration varied with and without Cr(VI) under both aerobic and anaerobic conditions. The Cr(VI) reduction data under anaerobic condition was fitted by a monod model to determine the bacterial kinetic parameters. The kinetic parameters determined by fitting the anaerobic experimental data were used to run a forward simulation for experiments conducted under aerobic conditions. The monod model was modified to account for an inhibition parameter for the Cr(VI) experiment at 260 mg l-1. All the parameters varied within a narrow range, and were distinct for different substrates. Our studies show that, successful in situ bioremediation of Cr(VI) is depended on the type of substrates (electron donors) and the concentration of Cr(VI) in geologic medium.     

含铁化合物对有机氯化物的脱氯处理技术研究

综述了钯 /铁、二硫化铁、硫化铁、三氧化二铁、绿锈等含铁化合物在降解六氯乙烷、四氯化碳、五氯乙烷、四氯乙烷、三氯乙烷、三氯乙烯、四氯乙烯等有机氯化物中的应用以及降解机理