Catalyzed dehalogenation of Delor 103 by sodium hydridoaluminate

The complete dechlorination of PCB liquid Delor 103 (42.6% Cl) to biphenyl has been effected in toluene with sodium dihydridobis(2-methoxyethoxo)aluminate (SDMA) in the presence of catalytic amounts of Ni(II) and Co(II) 2,4-pentanedionates at elevated temperatures. Changes in PCB congeners distribution during dechlorination were monitored by GC(ECD) and GC/MS, and the scheme of their transformation was proposed on the basis of site selectivity observed. A kinetic analysis of the reaction is presented.     

Chlorinated herbicide (triallate) dehalogenation by iron powder

The reductive degradation of a chlorinated herbicide by iron powder was investigated at lab scale. The studied substrate was triallate (S-2,3,3-trichloroallyl di-isopropyl thiocarbamate) which contains a trichloroethylene moiety potentially reducible by zero-valent iron. Degradation reactions were carried out in batch, at 25 degrees C, in the absence of oxygen, by contacting electrolytic iron powder (size range: 20-50 microm) with a triallate aqueous solution (2.5 mgl(-1)). Herbicide decay, corresponding evolutions of TOC, TOX and chloride ion release were regularly monitored throughout the reactions. Furthermore, the main degradation by-products were identified by HPLC/MS. The results showed that, after 5 days, herbicide degradation extent was about 97% and that the reaction proceeded through the formation of a dechlorinated alkyne by-product (S-2-propinyl di-isopropyl thiocarbamate) resulting from the complete dechlorination of triallate. The subsequent reduction of such an alkyne intermediate gave S-allyl di-isopropyl thiocarbamate as main end by-product. The identified by-products suggested that dechlorination took place mainly via reductive beta-elimination. However, as traces of dichloroallyl di-isopropyl thiocarbamate were also detected, a role, although minor, was assigned even to hydrogenolysis in the overall dechlorination process.     

废旧电路板与碳酸钙共热解脱卤的研究

采用热重分析仪和石英管式炉热解反应器,分别对以酚醛树脂为基板的废旧电路板和混合碳酸钙后的废旧电路板进行热解实验研究,着重考察了添加碳酸钙后的酚醛树脂基板废旧电路板热解特性及添加量不同对卤素脱除效果的影响。实验结果表明,碳酸钙的加入对废旧电路板的降解行为和热解油的基本组成没有明显的影响,但热解油的各组分含量有所差异;随着热解温度的提高或者CaCO₃含量的增多,卤素可以更多地由有机卤向无机卤转变并束缚在固体残渣中,由此得到较好的脱卤效果。当60%PR-WPCBs与40%CaCO₃共热解,热解油中的溴化物也减少了7.6% 。在600℃等量CaCO₃与PR-WPCBs共热解时生成75.6%无机卤,其中70.62%束缚于固体残渣中,可见达到较好的脱卤效果。     

Photolytic dehalogenation of the marine halogenated natural product Q1

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) has been detected in high-trophic level biota throughout the world. In this study we UV-irradiated Q1 in order to produce hexahalogenated 1'-methylbipyrroles (Cl(6)-MBPs). Q1 was transformed with half-lives of <5 min. Already after 5 min, all of the five existing Cl(6)-MBPs (H1-H5) were detected in the irradiated sample. Only one Cl(6)-MBP (2,3,3',4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-77, H2) has been previously described in the literature. H5 was identified as 2,3,3',4,4',5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-75) by a specific fragment ion detected by GC/ECNI-MS. Fractionations of the irradiation mixture by reversed-phase HPLC followed by (1)H NMR analysis led to the structure of H4, i.e. 2,3,3',4,4',5-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-74). H1 and H3 showed virtually identical (1)H NMR data. Therefore, it could not determined which of either isomers is 2,3,3',4,5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-76) and which is 2,3,4,4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-78). In addition, two pentachloro-MBPs (P1 and P3) could be traced back to MBP-62 and MBP-69. Cl(6)-MBPs were analyzed in whale blubber from Australia and skua adipose tissue from Antarctica. The marine mammals contained all Cl(6)-MBPs except for the most abundant in the irradiation experiment. The concentrations of the Cl(6)-MBPs amounted to 0.04-1.76% of the concentration of Q1. The highest concentrations of Cl(6)-MBP isomers in the biota samples were found for MBP-76, MBP-77, and MBP-78. These congeners appeared to be the most lipophilic ones owing to the highest retention time in RP-HPLC. Nevertheless, it remained unclear whether the Cl(6)-MBPs were actual halogenated natural products or environmental metabolites of Q1.     

Enhanced dehalogenation of halogenated methanes by bimetallic Cu/Al

A low-cost and high effective copper/aluminum (Cu/Al) bimetal has been developed for treatments of halogenated methanes, including dichloromethane, in near neutral and high pH aqueous systems. Bimetallic Cu/Al was prepared by a simple two-step synthetic method where Cu was deposited onto the Al surface. The presence of Cu on Al significantly enhanced rates of degradation of halogenated methanes and reduced toxic halogenated intermediates. The stability of Cu/Al was preliminarily studied by a multi-spiking batch experiment where complete degradation of carbon tetrachloride was achieved for seven times although the Cu/Al aging was found. Roles of Cu may involve protecting Al against an undesirable oxidation with water, enhancing reaction rates through the galvanic corrosion, and increasing the selectivity to a benign compound (i.e., methane). Kinetic analyses indicated that the activity of bimetallic Cu/Al was comparable to that of iron-based bimetals (e.g., palladized iron) and zero-valent metals. Bimetallic Cu/Al could be a promising reactive reagent for remediation of halogenated solvents-contaminated groundwater associated with high pH problems.     

Aerobic dehalogenation potentials of four bacterial species isolated from soil and sewage sludge

In Polar regions subject to acid precipitation, the spring flood period is swift and can be divided into three phases. In phase one, dilution and anion substitution by SO4 controls episodic acidification. Phase two is characterized by interaction of snowmelt water with the catchment. A combination of several factors contributes to declines in pH and ANC. In forest and wetland ecosystems, organic acids greatly contribute to the pH depression in the streams. In the coastal tundra and forest-tundra zones, "salt-effect" acidification predominantes. The increase in toxic forms of trace (Ni, Cu) and rare (Fe, Al, Mn) elements during pH depressions may create stress conditions for the fauna of polar fresh waters during a flood period.     

Biological and ecophysiological reactions of white wall rocket (Diplotaxis erucoides L.) grown on sewage sludge compost

We studied the effects of sewage sludge compost on white wall rocket (Diplotaxis erucoides L.) compared with mineral fertilization and control (without any fertilizer) in a greenhouse experiment. The plants grown on the compost-amended soil showed a different growth dynamic: a significant delay in flowering and a bigger root system. Both the compost and the fertilization treatments increased biomass and seed yield. Heavy metal (Cu, Cd, Zn, Ni) distribution within the plant was in the following order: roots > leaves > stems, except for zinc which was homogeneously distributed. The balance of mineral nutrition was not affected by treatments. Zinc was the trace element which was most taken up. Unlike many species of Brassicaceae, white wall rocket is not a hyperaccumulator. Although sewage sludge compost improved plant growth, delay in flowering shows that it is necessary to take precautions when spreading sewage sludge in natural areas.     

Carbon isotope fractionation during abiotic reductive dehalogenation of trichloroethene (TCE)

Dehalogenation of trichloroethene (TCE) in the aqueous phase, either on palladium catalysts with hydrogen as the reductant or on metallic iron, was associated with strong changes in delta13C. In general, the delta13C of product phases were more negative than those of the parent compound and were enriched with time and fraction of TCE remaining. For dehalogenation with iron, the delta13C of TCE and products varied from -42/1000 to +5/1000. For the palladium experiments, the final product, ethane, reached the initial delta13C of TCE at completion of the dehalogenation reaction. During dehalogenation, the carbon isotope fractionation between TCE and product phases was not constant. The variation in delta13C of TCE and products offers a new monitoring tool that operates independently of the initial concentration of pollutants for abiotic degradation processes of TCE in the subsurface, and may be useful for evaluation of remediation efficiency.     

Reductive dehalogenation of tetrabromobisphenol-A by sediment from a contaminated ephemeral streambed and an enrichment culture

This study was aimed at improving our understanding of the physiology of the microorganisms that reductively dehalogenate tetrabromobisphenol-A (TBBPA). Activity was followed in contaminated sediments from a polluted streambed as well as from fracture filling material underlying the stream. Reductive dehalogenation was observed in surface sediments but not in fracture filling samples from a depth of 3m. Likewise, anaerobic microbial activity, represented by sulphate reduction, was much higher in the surface sediment. In the culture enriched from the surface sediment, optimal microbial debromination of TBBPA took place at a salinity of 2% and 3% NaCl, temperature of 30 degrees Celsius, and pH of 7-8. Ethanol, pyruvate and the combination of hydrogen with acetate were the most suitable electron donors and carbon sources for this culture. Alternative electron acceptors like Fe(3+), SO(4)(2-), SO(3)(2-), NO(3)(-) and 2,4,6-tribromophenol inhibited TBBPA debromination. The debrominating bacteria were heat sensitive (80 degrees Celsius, for 10min) but were not inhibited by bromoethanesulphonate or molybdate. This study allowed optimisation of our culturing conditions, but was also important for understanding the factors which influence TBBPA debromination in situ.     

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.     

Heterogeneous reductive dehalogenation of PCB contaminated transformer oil and brominated diphenyl ethers with zero valent iron

Reductive dechlorination and debromination of halogenated biphenyls (PCBs) and diphenyl ethers (PBDEs) occurs efficiently at moderately elevated temperatures (350-600 °C) with zero valent iron (iron powder) in a nitrogen atmosphere. The proton donors tested were waste transformer oil, iso-octane, and n-decane. Observation of production of biphenyl and diphenyl ether and their condensation products indicates that the reaction is not simple pyrolysis, but a reduction. No halogenated organic products are observed.     

Simulated and experimental evaluation of factors affecting the rate and extent of reductive dehalogenation of chloroethenes with glucose

Carbohydrates such as molasses are being added to aquifers to serve as electron donors for reductive dehalogenation of chloroethenes. Glucose, as a model carbohydrate, was studied to better understand the processes involved and to evaluate the effectiveness for dehalogenation of different approaches for carbohydrate addition. A simulation model was developed and calibrated with experimental data for the reductive dehalogenation of tetrachloroethene to ethene via cis-1,2-dichloroethene. The model included fermentors that convert the primary donor (glucose) into butyrate, acetate and hydrogen, methanogens, and two separate dehalogenator groups. The dehalogenation groups use the hydrogen intermediate as an electron donor and the different haloethenes as electron acceptors through competitive inhibition. Model simulations suggest first that the initial relative population size of dehalogenators and H(2)-utilizing methanogens greatly affects the degree of dehalogenation achieved. Second, the growth and decay of biomass from soluble carbohydrate plays a significant role in reductive dehalogenation. Finally, the carbohydrate delivery strategies used (periodic versus batch addition and the time interval between periodic addition) greatly affect the degree of dehalogenation that can be obtained with a given amount of added carbohydrate.     

Efficient dehalogenation of automobile shredder residue in NaOH/ethylene glycol using a ball mill

We investigated the effectiveness of sodium hydroxide/ethylene glycol (NaOH/EG) for dehalogenation of automobile shredder residue (ASR) using a ball mill. Efficient dehalogenation was achieved at atmospheric pressure by combining the use of EG (196 degrees C b.p.) as a replacement solvent for NaOH with ball milling, which improved contact between ASR and OH(-) in solution. Moderate NaOH concentrations and increased ball mill rotation speeds produced high dechlorination that was not significantly affected by the weight ratio of ASR to EG. NaOH/EG dechlorination increased with temperature with an apparent activation energy of 50 kJ mol(-1) confirming that the reaction proceeded under chemical reaction control. The modified shrinking-core model was appropriate to explain the dechlorination process. Low chloro levels in our NaOH/EG-treated ASR suggested that this material could be used for feedstock recycling and the wet process may be applicable for dehalogenation of other important waste streams.     

Continuous-flow column study of reductive dehalogenation of PCE upon bioaugmentation with the Evanite enrichment culture

A continuous-flow anaerobic column experiment was conducted to evaluate the reductive dechlorination of tetrachloroethene (PCE) in Hanford aquifer material after bioaugmentation with the Evanite (EV) culture. An influent PCE concentration of 0.09 mM was transformed to vinyl chloride (VC) and ethene (ETH) within a hydraulic residence time of 1.3 days. The experimental breakthrough curves were described by the one-dimensional two-site-nonequilibrium transport model. PCE dechlorination was observed after bioaugmentation and after the lactate concentration was increased from 0.35 to 0.67 mM. At the onset of reductive dehalogenation, cis-dichloroethene (c-DCE) concentrations in the column effluent exceeded the influent PCE concentration indicating enhanced PCE desorption and transformation. When the lactate concentration was increased to 1.34 mM, c-DCE reduction to vinyl chloride (VC) and ethene (ETH) occurred. Spatial rates of PCE and VC transformation were determined in batch-incubated microcosms constructed with aquifer samples obtained from the column. PCE transformation rates were highest in the first 5 cm from the column inlet and decreased towards the column effluent. Dehalococcoides cell numbers dropped from approximately 73.5% of the total Bacterial population in the original inocula, to about 0.5% to 4% throughout the column. The results were consistent with estimates of electron donor utilization, with 4% going towards dehalogenation reactions.     

The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries

Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.     

N-甲基咪唑配体络合金属Cu(I)催化剂对水中2,4-二甲氧基溴苯还原脱溴

合成了以N-甲基咪唑为配体,Cu为活性中心的络合金属多相催化剂Cu(I)-NHC-SBA-15。通过1H-NMR、13C-NMR、有机元素分析和FTIR对各步合成反应产物结构经行了鉴定;用SEM、N2吸附脱附等方法对催化剂进行了表征;用ICP测定了催化剂Cu含量。对催化剂催化2,4-二甲氧基溴苯还原脱溴活性进行了测试。在反应时间为24 h,通过正交实验和单因素实验,考察了催化剂用量、反应温度、还原剂用量等因素对脱溴率的影响,并确定了最佳反应条件:催化剂用量为0.05 g、水合肼用量为2 mL、反应温度为80℃,脱溴效果较好,脱溴率达到98.5%。对催化剂重复使用进行了初步研究。对催化反应动力学进行了初步研究,结果表明,该多相催化反应是由表面反应速度控制,并符合一级动力学反应。对反应机理进行了初步探讨。     

SO2的生物监测与防治

SO2是我国大气的主要污染物之一，一般大气中的SO2多采用化学法监测，而生物对SO2的监测具有独到的作用，文中就SO2对人类的危害和生物监测及防治进行了初探。