Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Microbial transformation and degradation of polychlorinated biphenyls

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H(2) to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products.     

Chemical dechlorination of polychlorinated biphenyls (PCBs) from dielectric oils

We studied the chemical dechlorination of the polychlorinated biphenyls (PCBs) in some dielectric oils via nucleophilic substitution of the chloro atoms by polyethylene alkoxide. The influence of temperature, ultrasounds, polyethylene glycol (PEG) and base type was investigated. Our findings show that dechlorination of PCBs by chemical treatment is effective at moderate temperature (90–100°C) and is strongly dependent on the nature of matrix oil. Stirring affects the process yield by influencing the homogeneity of the oil/glycol two-phase system. Ultrasounds can improve the process efficiency by making operating conditions less severe. Selected article from the 6th European Meeting on Environmental Chemistry, University of Belgrade, Serbia and Montenegro organized by Prof. Dr. Branimir Jovancicevic ().     

Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

Dechlorination of 1,2,4-trichlorobenzene in the sediment of Ise Bay

The relation between dechlorination activities of 1,2,4-trichlorobenzene and anaerobic microbial activity were studied in the sediment collected at three sites in Ise Bay in Japan. The degradation rate of spiked 1,2,4-trichlorobenzene (3nmol ml⁻¹) ranged from 15 to 35 pmol day⁻¹ ml⁻¹ wet sediment and about 1/3 to 1/2 of degraded the trichlorobenzene was recovered as dechlorinated products. Among the dichlorobenzenes, the 1,2-isomer had the highest and 1,3-isomer had the lowest production rate. Comparing the three sampling sites, the trichlorobenzene degradation and dichlorobenzenes production rates were related to the sulfate reducing activity for the unit number of sulfate reducing bacteria. Production rates of dichlorobenzenes were completely inhibited by adding molybdate (20 mM), nitrate (60 mM), and formaldehyde solution (4 %). These results indicated that dechlorination activity in the Ise Bay sediment was supported by sulfate reduction activity in the sediment, and not supported by any other anaerobic microbial activity.     

Removal of 2-ClBP from soil–water system using activated carbon supported nanoscale zerovalent iron

We explored the feasibility and removal mechanism of removing 2-chlorobiphenyl(2-Cl BP)from soil–water system using granular activated carbon(GAC) impregnated with nanoscale zerovalent iron(reactive activated carbon or RAC).The RAC samples were successfully synthesized by the liquid precipitation method.The mesoporous GAC based RAC with low iron content(1.32%) exhibited higher 2-Cl BP removal efficiency(54.6%) in the water phase.The result of Langmuir–Hinshelwood kinetic model implied that the different molecular structures between 2-Cl BP and trichloroethylene(TCE) resulted in more difference in dechlorination reaction rates on RAC than adsorption capacities.Compared to removing2-Cl BP in the water phase,RAC removed the 2-Cl BP more slowly in the soil phase due to the significant external mass transfer resistance.However,in the soil phase,a better removal capacity of RAC was observed than its base GAC because the chemical dechlorination played a more important role in total removal process for 2-Cl BP.This important result verified the effectiveness of RAC for removing 2-Cl BP in the soil phase.Although reducing the total RAC removal rate of 2-Cl BP,soil organic matter(SOM),especially the soft carbon,also served as an electron transfer medium to promote the dechlorination of 2-Cl BP in the long term.     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

Removal of trichloroethylene from soil using the hydration of calcium oxide

Quicklime addition to soil at a remediation site was observed to sufficiently reduce TCE levels, but the cause of the removal could not be confirmed with the field data collected. Potential mechanisms for CaO treatment of trichloroethylene (TCE) in soil include degradation and volatilization. Since earlier studies found TCE degradation to occur during the hydration of CaO under conditions where volatilization was limited, research was conducted on mechanisms of TCE removal from soil by CaO application under conditions where volatilization was allowed to occur. TCE volatilization in soil treated with 0%, 5%, 10%, and 20% CaO doses was measured in experiments where the degree of volatilization could be tracked. The total TCE removal from soil spiked with TCE at CaO doses from 5% to 20% ranged from 97% to 99% of the initial TCE mass. Volatilization accounted for 64.4-92.5% of the TCE removal, with unrecovered TCE and TCE degradation accounting for the remaining fraction. The greater heat encountered with higher CaO doses helped minimize obstacles to TCE volatilization, such as high soil organic and clay content. Treatment with a 20% CaO dose, however, led to the formation of byproducts such as dichloroacetylene. TCE degradation to dichloroacetylene at the 20% CaO dose ranged from 2.7% to 6.4% of the initial TCE. Volatilization was concluded to be the dominant process for TCE removal from soil during CaO treatment.     

Soil- and surfactant-enhanced reductive dechlorination of carbon tetrachloride in the presence of Shewanella putrefaciens 200

Sorption of organic contaminants to soils has been shown to limit bioavailability and biodegradation in some systems. Use of surfactants has been proposed to reverse this effect. In this study, the effects of a high organic carbon content soil and a nonionic surfactant (Triton X-100) on the reductive dechlorination of carbon tetrachloride (CCl₄) were examined in anaerobic systems containing Shewanella putrefaciens. Although more than 70% of the added CCl₄ was sorbed to the soil phase in these systems, the reductive dechlorination of CCl₄ was not diminished. Rather, rates of CCl₄ dechlorination in systems containing soil were enhanced relative to systems containing non-sorptive sand slurries. This enhancement was also observed in sterile soil slurries to which a chemical reductant, dithiothreitol was added. It appears that the organic soil used in these experiments contains some catalytic factor capable of transforming CCl₄ in the presence of an appropriate chemical or microbial reductant. The addition of Triton X-100 to sand and soil slurries containing S. putrefaciens resulted in increased CCl₄ degradation in both systems. The effect of Triton could not be explained by: (i) surfactant induced changes in the distribution of CCl₄, (i.e. decreased sorption) or the rate of CCl₄ desorption; (ii) a direct reaction between Triton and CCl₄; or (iii) increased cell numbers resulting from use of the surfactant as a substrate. Rather, it appears that Triton X-100 addition resulted in lysis of bacterial cells, a release of biochemical reductant, and enhanced reductive transformation of CCl₄. These results provide insights to guide the development of more effective direct or indirect bioremediation strategies.     

化工制药工艺残渣燃烧过程固氯研究

采用管式固定床反应器对化工制药工艺残渣的燃烧分解进行了实验研究,进一步通过加入氧化钙/碳酸钙来防止燃烧过程残渣中氯的释放.实验结果表明,残渣在燃烧时氯主要以氯化氢形式排出,加入固氯剂后能有效地抑制氯化氢的生成,且固氯效果随着钙化物投加量的增加而明显提高.当氧化钙/残渣比(质量比)达到0.8时,固氯率可达97%以上;当碳酸钙/残渣比(质量比)提高到2.0时,固氯率为76%.与此对应的Ca/Cl摩尔比分别为30和40.继续增加钙投加量,固氯效果基本不变.同时发现添加一定量的木屑在助燃的同时有助于提高固氯效果.