零价铁与厌氧微生物协同还原地下水中的硝基苯

通过间歇式实验,考察了零价铁与厌氧微生物协同还原地下水中硝基苯的效果。实验结果表明,由零价铁腐蚀为厌氧微生物提供H2电子供体还原硝基苯的效果明显优于零价铁和微生物单独作用,硝基苯去除率分别提高21.8%和57.0%。弱酸性条件有利于协同反应进行,当初始pH为5.0和6.0时,4 d后硝基苯去除率比初始pH为7.0时的提高74.4%和35.2%。增加零价铁投加量可提高协同还原的效果,零价铁最佳投加量为250 mg/L。零价铁腐蚀产生的Fe2+无法作为电子供体被微生物利用,但可作为无机营养元素促进协同过程。由于零价铁产H2速率受表面覆盖物影响不明显,在地下水修复过程中可保证协同效果并延长零价铁的使用寿命。     

超声波/零价铁降解对硝基苯胺的试验研究

对在超声波、零价铁和超声波/零价铁(U/Fe0)等体系中对硝基苯胺的降解规律进行了研究。研究结果表明,对硝基苯胺在超声波作用下,降解规律符合一级反应动力学模型,但超声波对高浓度的对硝基苯胺降解效果较差。在U/Fe0体系中,超声波和零价铁对降解对硝基苯胺具有协同作用,对硝基苯胺降解速率显著提高。降解机理显示,对硝基苯胺在零价铁表面上发生原电池反应,被还原为对苯二胺,在超声波作用下进一步降解。在U/Fe0体系中添加Cu2+,形成Fe/Cu原电池,可进一步促进对硝基苯胺的降解速率,降解效率优于铸铁屑形成的Fe/C原电池。     

Catalytic dechlorination kinetics of p-dichlorobenzene over Pd/Fe catalysts

p-Dichlorobenzene (p-DCB) was dechlorinated using Pd/Fe bimetallic catalytic reductants synthesized by chemical deposition. Batch experiments demonstrated that the Pd/Fe bimetallic particles could effectively dechlorinate p-DCB, p-DCB and its intermediate chlorobenzene were removed completely at a Pd loading of 0.02% (weight ratio of Pd to Fe) and Pd/Fe power to solution ratio about 4g 75 ml-1 in 90 min. Dechlorination was affected by various factors such as the reaction temperature, pH, Pd loading percentage over Fe and the introduction of Pd/Fe catalysts et al. Chlorobenzene represents partially stable dechlorinated intermediates in the generation of benzene and part of p-DCB was dechlorinated to benzene indirectly on the surface of Pd/Fe. The dechlorination of p-DCB took place on the surface of the Pd/Fe bimetallic particles in a pseudo-first-order reaction, the activation energy of the dechlorination reaction was determined to be 80.0 kJ mol-1 at the temperature range of 287-313 K.     

Iron and organo-bentonite for the reduction and sorption of trichloroethylene

Hybrid barriers using dechlorination and immobilization were studied to remove trichloroethylene (TCE) in this study. Hybrid barriers of iron filings and organo (hexadecyltrimethylammonium, HDTMA)-bentonite were simulated in columns to assess the performance of the hybrid barriers. TCE reduction rate for the mixture of zero valent iron (ZVI) and HDTMA-bentonite was approximately seven times higher than that for ZVI, suggesting the reduction of TCE was accelerated when HDTMA-bentonite was mixed with ZVI. For the column of two separate layers of iron and HDTMA-bentonite, TCE reduction rate was nearly similar to that for ZVI alone, but the partition coefficient (Kd) was 4.5 times higher than that for ZVI only. TCE was immobilized in the first layer with HDTMA-bentonite due to sorption, and then dechlorinated in the second layer with iron filings due to reduction. The HDTMA-bentonite and minimally-desorbed HDTMA from the organo-bentonite are believed to contribute the increase in TCE concentration on iron surface so that more TCE could be available for reduction. Therefore, the incorporation of HDTMA-bentonite into ZVI not only can effectively retard the transport of chlorinated organic contaminants from landfill leachate or oil shock in subsurface environment, also can expedite the reduction rate of TCE.     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

Catalytic amination and dechlorination of para-nitrochlorobenzene (p-NCB) in water over palladium-iron bimetallic catalyst

Chemical treatment of para-nitrochlorobenzene (p-NCB) by palladium/iron (Pd/Fe) bimetallic particles represents one of the latest innovative technologies for the remediation of contaminated soil and groundwater. The amination and dechlorination reaction is believed to take place predominantly on the surface site of the Pd/Fe catalysts. The p-NCB was first transformed to p-chloroaniline (p-CAN) then quickly reduced to aniline. 100% of p-NCB was removed in 30 min when bimetallic Pd/Fe particles with 0.03% Pd at the Pd/Fe mass concentration of 3g 75 ml(-1) were used. The p-NCB removal efficiency and the subsequent dechlorination rate increased with the increase of bulk loading of palladium and Pd/Fe. As expected, p-NCB removal efficiency increased with temperature as well. In particular, the removal efficiency of p-NCB was measured to be 67%, 79%, 80%, 90% and 100% for reaction temperature 20, 25, 30, 35 and 40 degrees C, respectively. Our results show that no other intermediates were generated besides Cl(-), p-CAN and aniline during the catalytic amination and dechlorination of p-NCB.     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

Removal of thiobencarb in aqueous solution by zero valent iron

A cost-effective method with zero valent iron (ZVI) powder was developed for the purification of thiobencarb (TB)-contaminated water. The removal treatment was performed in the batch system. A sample solution of 10 ml containing 10 microg ml(-1) of TB could be almost completely treated by 100mg of ZVI at 25 degrees C for 12h of treatment time. Since the formation of chloride ion in the aqueous solution during the treatment of TB was observed, the removal of TB with ZVI may contain two processes: reduction (degradation) and adsorption. Because the present treatment for TB is simple, easy handling and cheap, the developed technology with ZVI can contribute to the treatment of agricultural wastewaters.     

Mechanisms of NOx removal from flue gas by zero valent iron

Chemical reaction between nitric oxide (NO) andzero valent iron (ZVI) was studied in a packed-bed column process with high temperatures based on ZVI strong reducing abilities. For six controlled temperatures of 523-773 K and 400 ppm of NO (typical flue gas temperature and concentration), under short empty bed contacttime ([EBCT] 0.0226-0.0679 sec), NO was completely removed for temperature of 573-773 K but not for 523 K. Break-through curves were conducted for the five working temperatures, and the results indicated that NO reductions by ZVI were varied from 2 to 26.7 mg NO/g ZVI. Higher temperature and longer EBCT achieved better NO removal efficiency. X-ray diffraction (XRD) and electron spectroscopy for chemical analysis (ESCA) were conducted to analyze the crystal structure and oxidation state of the reacted ZVI. Three layers of iron species were detected by XRD: ZVI, Fe3O4, and Fe2O3. ZVI was the most prevalent species, and Fe3O4 and Fe2O3 were less from the XRD analysis. By ESCA, the oxidation state on the reacted ZVI surface was determined, and the species was identifled as Fe2O3, which is the most oxidizing species for iron. Therefore, three layers from the ZVI core to the ZVI surface can be identified: ZVI, Fe3O4, and Fe2O3. Combining the results from XRD and ESCA, the mechanisms for ZVI and NO can be proposed as two consecutive reactions from lower oxidation state (ZVI) in the core to higher oxidation state on the iron surface (Fe2O3): 3Fe + 4NO<--(high temperature)-->Fe3O4 + 2N2 (A1), 4Fe3O4 + 2NO<--(high temperature)-->6Fe2O3 + N2* (A2) Because there was only <5% ZVI used to remove NO comparing to theoretical ZVI used based on the proposed stoichiometry, it can be concluded that the heterogeneous reaction only occurred on the ZVI surface instead of on bulk of the ZVI.     

钯/铝双金属体系对3-氯酚的脱氯降解

研究了钯/铝双金属体系对水相中3-氯酚的催化脱氯降解效果,通过置换沉积制备了钯/铝双金属颗粒,考察了该双金属颗粒的稳定性以及溶液pH和钯负载量对脱氯效果的影响。结果表明,pH在4.0以下的酸性条件,钯负载量在1.43%时,可实现水相中3-氯酚的有效脱氯,反应30 min后0.389 mmol/L的3-氯酚转化率可达99%以上,产物主要为苯酚,而钯/铝颗粒在重复测试中能保持较好的稳定性,这与铝基材表面自发形成的氧化膜有关。钯/铝材料表征的结果表明,钯颗粒高度分散在铝基材表面,并极大地提高了铝基材的表面积,从而有助于后续的脱氯反应。     

Fluidized zero valent iron bed reactor for nitrate removal

A fluidized zero valent iron (ZVI) reactor is examined for nitrate reduction. Using the system, the pH of solution can be maintained at optimal conditions for rapid nitrate reduction. For hydraulic retention times of 15 min, the nitrate reduction efficiency increases with increasing ZVI dosage. At ZVI loadings of 33 gl-1, results indicate that the nitrate removal efficiency increases from less than 13% for systems without pH control to more than 92% for systems operated at pH of 4.0. By maintaining pH at 4.0, we are able to decrease the hydraulic retention time to 3 min and still achieve more than 87% nitrate reduction. The recovery of total nitrogen added as nitrate, ammonium, and nitrite was less than 50% for the system operated at pH4.0, and was close to 100% for a system without pH control. The possibility of nitrate and ammonium adsorption onto iron corrosion products was ruled out by studying the behavior of their adsorption onto freshly hydrous ferric oxide at variable pH. Results indicate the probable formation of nitrogen gas species during reaction in pH4.0.     

Simultaneous adsorption and degradation of γ-HCH by nZVI/Cu bimetallic nanoparticles with activated carbon support

Cu amended zero valent iron bimetallic nanoparticles were synthesized by doping Cu on the surface of iron. They were incorporated with granular activated carbon (AC) to prepare supported particles (AC-Fe⁰-Cu), which were used to remove γ-HCH. Cu on the surface of iron enhanced the dechlorination activity of Fe⁰. The dechlorination rate constant (k_obs) increased with the Cu loading on the surface of iron and the maximum was achieved with 6.073% Cu. AC as a support was effective for increasing the dispersion of the nanoparticles and avoiding the agglomeration of the metallic nanoparticles. The simultaneous adsorption of γ-HCH on AC accelerated the degradation rate of γ-HCH by the bimetals. After reaction for 165 min, around 99% of γ-HCH was removed by the solids of AC-Fe⁰-Cu. In addition, AC could adsorb the degradation products. The degradation of γ-HCH was mainly through dehydrochlorination and dichloroelmination based on the intermediate products detected by GC/MS.     

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.     

Enhanced reductive dechlorination of polychlorinated biphenyl-contaminated soil by in-vessel anaerobic composting with zero-valent iron

Anaerobic dechlorination is an effective degradation pathway for higher chlorinated polychlorinated biphenyls (PCBs). The enhanced reductive dechlorination of PCB-contaminated soil by anaerobic composting with zero-valent iron (ZVI) was studied, and preliminary reasons for the enhanced reductive dechlorination with ZVI were investigated. The results show that the addition of nanoscale ZVI can enhance dechlorination during in-vessel anaerobic composting. After 140 days, the average number of removed Cl per biphenyl with 10 mg g^?1 of added nanoscale ZVI was 0.63, enhancing the dechlorination by 34 % and improving the initial dechlorination speed. The ZVI enhances dechlorination by providing a suitable acid base environment, reducing volatile fatty acid inhibition and stimulating the microorganisms. The C/N ratios for treatments with the highest rate of ZVI addition were smaller than for the control, indicating that ZVI addition can promote compost maturity.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH^? · pH^?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg^?1 (6.21 × 10^?7–3.09 × 10^?6 mol atrazine · g^?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10^?2?7.04 × 10^?2 d^?1 for the atrazine-spiked sediments.     

Regeneration of iron for trichloroethylene reduction by Shewanella alga BrY

Zero valent iron (ZVI), the primary reactive material in several permeable reactive barriers, is often oxidized to ferrous or ferric iron, resulting in decreased reactivity with time. Iron reducing bacteria can reconvert the ferric iron to its ferrous form, prolonging the reduction of chlorinated organic contaminants. In this study, the reduction of Fe(II,III) oxide and Fe(III) oxide by a strain of iron reducing bacteria of the group Shewanella alga BrY(S. alga BrY) was observed in both aqueous and solid phases. S. alga BrY preferentially reduced dissolved ferric iron over the solid ferric iron. In the presence of iron oxide the Fe(II) ions reduced by S. alga BrY efficiently reduced trichloroethylene (TCE). On the other hand, Fe(II) produced by S. alga BrY covered the reactive surfaces of ZVI iron filings and inhibited the reduction of TCE by ZVI. The formation of precipitates on the iron oxide or Fe0 surface was confirmed by scanning electron microscopy. The results suggest that iron-reducing bacteria in the oxidized Fe0 barriers can enhance the removal rate of chlorinated organic compounds and influence on the long-term performance of Fe0 reactive barriers.     

Structure relationship for catalytic dechlorination rate of dichlorobenzenes in water

Three isomers of dichlorobenzene (o-, m- and p-DCB) were dechlorinated by Pd/Fe catalyst in aqueous solutions through catalytic reduction. The dechlorination reaction took place on the surface site of the catalyst via a pseudo-first-order kinetics, and resulted in benzene as the final reduction product. The rate constants of the reductive dechlorination for the three dichlorobenzenes (DCBs) in the presence of Pd/Fe as a catalyst were measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy of the formation of DCBs. The reaction rate constant for o-, m- and p-DCBs in the presence of 0.020% (w/w) Pd/Fe at 25 °C was determined to be 0.0213, 0.0223, and 0.0254 min⁻¹, respectively. While the activation energy of each dechlorination reaction was measured to be 102.5, 96.6 and 80.0 kJ mol⁻¹ for o-, m- and p-DCBs, respectively. The results demonstrated that p-DCBs were reduced more easily than o- or m-DCBs, and the order of the tendency of the dechlorination was p-DCB > m-DCB > o-DCB. The presented data show the catalytic reduction using Pd/Fe as a catalyst is a fast and easy approach for the dechlorination of DCBs.     

Making chlorine greener: performance of alternative dechlorination agents in wastewater

The residual chlorine in chlorine-disinfected and dechlorinated wastewater was characterized using a liquid chromatograph that was switched between reversed-phase separation and flow injection analysis modes, permitting measurement of fractionated and total residual chlorine, respectively. Residuals were detected in the effluent of an operating wastewater treatment plant employing chlorine disinfection and sulfite dechlorination. Despite dechlorination, an estimated total residual chlorine of 3 microM (0.2 ppm as Cl2) was detected in the effluent. To improve dechlorination effectiveness, four alternative agents (ascorbic acid, iron, sulfite plus iodide mediator, thiosulfate) were compared to sulfite on laboratory-chlorinated wastewater. Listed in order of decreasing relative effectiveness, we found: iron metal > sulfite plus iodide approximately = thiosulfate > sulfite > ascorbic acid. Only the iron metal column was completely effective at rapidly removing all traces of residual chlorine.     

Hybrid zero valent iron (ZVI)/H2O2 oxidation process for landfill leachate treatment with novel nanosize metallic calcium/iron composite

A novel nanosize metallic calcium/iron dispersed reagent was synthesized and tested as coagulant/catalyst in a hybrid zero valent iron (ZVI)/H₂O₂ oxidation process to treat leachate. Two different types of leachates, one from municipal solid waste (MSW) tipping hall (MSWIL) and second from an MSW landfill site (MSWLL), were collected and characterized. The morphology, elemental composition, and mineral phases of the nano-Ca/CaO and nano-Fe/Ca/CaO were characterized by scanning electron microscopy–electron dispersive spectroscopy (SEM-EDS) and x-ray powder diffraction (XRD) analysis. The coagulation process with 2.5 g L^?1 nano-Ca/CaO attained 64.0, 56.0, and 20.7% removal of color, chemical oxygen demand (COD), and total suspended solids (TSS) in MSWLL. With only 1.0 g L^?1 of nano-Fe/Ca/CaO, relatively high color, COD and TSS removal was achieved in MSWLL at 67.5, 60.2, and 37.7%, respectively. The heavy metal removal efficiency reached 91–99% after treatment with nano-Fe/Ca/CaO in both leachate samples. The coupling process, using 1.0 g L^?1 of nano-Fe/Ca/CaO and 20 mM H₂O₂ doses, achieved enhancement removal of color, COD, and TSS, up to 95%, 96%, and 66%, respectively, without initial pH control. After this treatment, the color, COD, TSS, and heavy metals were significantly decreased, fitting the Korean discharge regulation limit. A hybrid coupled zero valent iron (ZVI)/H₂O₂ oxidation process with novel nanosized metallic calcium/iron dispersed reagent proved to be a suitable treatment for dealing with leachate samples.

Implications: Conventional treatments (biological or physicochemical) are not sufficient anymore to reach the level of purification needed to fully reduce the negative impact of landfill leachates on the environment. This implies that new treatment alternatives species must be proposed. A coupled zero valent iron (ZVI)/H₂O₂ oxidation process proved to be a suitable treatment for dealing with leachate samples. Coagulation with nFe/Ca/CaO allows 91–99% of heavy metals removal. The coupled coagulation–oxidation process by nFe/Ca/CaO reveals excellent ability to treat leachate. After coupled treatment the color, COD, and TSS were also much lower than the discharge regulation limit.