细菌Rieske型非血红素铁加氧酶研究进展

细菌Rieske型非血红素铁加氧酶是催化芳香化合物好氧降解第一步反应的酶,能够激发好氧环境下大量芳香或取代芳香化合物的生物降解,同时还可作为有机化合物的合成子.这是一类新型且丰富的酶资源,在受污环境的生物修复方面有着巨大的潜力,并且符合“绿色化学”的要求.本文综述了该类酶的分类、晶体结构、作用机理及其基因改造等最新研究进展. 图4表1参17     

Scrap Iron Filings assisted nitrate and phosphate removal in low C/N waters using mixed microbial culture

• Microbes enhance denitrification under varying DO concentrations and SIF dosages. • Abiotic nitrate reduction rates are proportional to SIF age and dosage. • Over 80% of the simultaneously loaded NO₃⁻-N and PO₄³⁻ is removed biologically. This study focuses on identifying the factors under which mixed microbial seeds assist bio-chemical denitrification when Scrap Iron Filings (SIF) are used as electron donors and adsorbents in low C/N ratio waters. Batch studies were conducted in abiotic and biotic reactors containing fresh and aged SIF under different dissolved oxygen concentrations with NO₃⁻-N and/or PO₄^3- influent(s) and their nitrate/phosphate removal and by-product formations were studied. Batch reactors were seeded with a homogenized mixed microbial inoculum procured from natural sludges which were enriched over 6 months under denitrifying conditions in the presence of SIF. Results indicated that when influent containing 40 mg/L of NO₃⁻-N was treated with 5 g SIF, 79.9% nitrate reduction was observed in 8 days abiotically and 100% removal was accomplished in 20 days when the reactor was seeded. Both abiotic and seeded reactors removed more than 92% PO₄³⁻ under high DO conditions in 12 days. Abiotic and biochemical removal of NO₃⁻-N and abiotic removal of PO₄³⁻ were higher under independent NO₃⁻-N/PO₄³⁻ loading, while 99% PO₄^3- was removed biochemically under combined NO₃⁻-N and PO₄³⁻ loading. This study furthers the understandings of nitrate and phosphate removal in Zero Valent Iron (ZVI) assisted mixed microbial systems to encourage the application of SIF-supported bio-chemical processes in the simultaneous removals of these pollutants.     

Synergistic effects of sodium hypochlorite disinfection and iron-oxidizing bacteria on early corrosion in cast iron pipes

• The early corrosion process in the cast iron pipes was investigated. • The increase of NaOCl (<0.75 mg/L) accelerated the cast iron corrosion. • Biocorrosion caused by IOB could be divided into three stages in the early stage. • Synergistic and antagonistic effects exist between residual chlorine and IOB. Corrosion in drinking water distribution systems (DWDSs) may lead to pipe failures and water quality deterioration; biocorrosion is the most common type. Chlorine disinfectants are widely used in DWDSs to inhibit microorganism growth, but these also promote electrochemical corrosion to a certain extent. This study explored the independent and synergistic effects of chlorine and microorganisms on pipeline corrosion. Sodium hypochlorite (NaOCl) at different concentrations (0, 0.25, 0.50, and 0.75 mg/L) and iron-oxidizing bacteria (IOB) were added to the reaction system, and a biofilm annular reactor (BAR) was employed to simulate operational water supply pipes and explain the composite effects. The degree of corrosion became severe with increasing NaOCl dosage. IOB accelerated the corrosion rate at an early stage, after which the reaction system gradually stabilized. When NaOCl and IOB existed together in the BAR, both synergistic and antagonistic effects occurred during the corrosion process. The AOC content increased due to the addition of NaOCl, which is conducive to bacterial regrowth. However, biofilm on cast iron coupons was greatly influenced by the disinfectant, leading to a decrease in microbial biomass over time. More research is needed to provide guidelines for pipeline corrosion control.     

Cadmium removal mechanistic comparison of three Fe-based nanomaterials: Water-chemistry and roles of Fe dissolution

● nZVI, S-nZVI, and nFeS were systematically compared for Cd(II) removal. ● Cd(II) removal by nZVI involved coprecipitation, complexation, and reduction. ● The predominant reaction for Cd(II) removal by S-nZVI and nFeS was replacement. ● A simple pseudo-second-order kinetic can adequately fit Fe(II) dissolution. Cadmium (Cd) is a common toxic heavy metal in the environment. Taking Cd(II) as a target contaminant, we systematically compared the performances of three Fe-based nanomaterials (nano zero valent iron, nZVI; sulfidated nZVI, S-nZVI; and nano FeS, nFeS) for Cd immobilization under anaerobic conditions. Effects of nanomaterials doses, initial pH, co-existing ions, and humic acid (HA) were examined. Under identical conditions, at varied doses or initial pH, Cd(II) removal by three materials followed the order of S-nZVI > nFeS > nZVI. At pH 6, the Cd(II) removal within 24 hours for S-nZVI, nFeS, and nZVI (dose of 20 mg/L) were 93.50%, 89.12% and 4.10%, respectively. The fast initial reaction rate of nZVI did not lead to a high removal capacity. The Cd removal was slightly impacted or even improved with co-existing ions (at 50 mg/L or 200 mg/L) or HA (at 2 mg/L or 20 mg/L). Characterization results revealed that nZVI immobilized Cd through coprecipitation, surface complexation, and reduction, whereas the mechanisms for sulfidated materials involved replacement, coprecipitation, and surface complexation, with replacement as the predominant reaction. A strong linear correlation between Cd(II) removal and Fe(II) dissolution was observed, and we proposed a novel pseudo-second-order kinetic model to simulate Fe(II) dissolution.     

A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene

The remediation of nitroaromatic contaminated groundwater is sometimes difficult because nitroaromatic compounds are resistant to biodegradation and, when they do transform, the degradation of the products may also be incomplete. A simple nitroaromatic compound, nitrobenzene, was chosen to assess the feasibility of an in situ multi-zone treatment system at the laboratory scale. The proposed treatment system consists of a zero valent granular iron zone to reduce nitrobenzene to aniline, followed by a passive oxygen release zone for the aerobic biodegradation of the aniline daughter product using pristine aquifer material from Canadian Forces Base (CFB) Borden, Ontario, as an initial microbial source. In laboratory batch experiments, nitrobenzene was found to reduce quickly in the presence of granular iron forming aniline, which was not further degraded but remained partially sorbed onto the granular iron surface. Aniline was found to be readily biodegraded with little metabolic lag under aerobic conditions using the pristine aquifer material. A sequential column experiment, containing a granular iron reducing zone and an aerobic biodegradation zone, successively degraded nitrobenzene and then aniline to below detection limits (0.5 microM) without any noticeable reduction in hydraulic conductivity from biofouling, or through the formation of precipitates.     

超声波／纳米铁协同降解氯代苯酚的试验

通过间歇试验对超声波／纳米铁协同降解氯代苯酚（CPs）废水进行了研究，结果表明，超声波／纳米铁协同对CPs的降解率明显高于单纯超声波和单纯纳米铁的降解率；协同体系、单纯超声波和单纯纳米铁降解CPs均符合准一级反应动力学，协同体系的降解速率较单纯超声波提高了5．1-5．6倍，较单纯纳米铁提高了17．7～21倍，并且比它们的几何迭加值高4倍以上；氯代苯酚降解的准一级速率常数和降解率满足以下规律：PEP〉2，4，5-TCP〉2，4-DCP〉3-CP；探讨了混合废水的降解：在混合废水体系中，结构易裂解的优先降解，然后为浓度高的优先降解。     

Sodium Persulfate Oxidation for the Remediation of Chlorinated Solvents (USEPA Superfund Innovative Technology Evaluation Program)

This study has been conducted at the University of Connecticut (UCONN) in connection with the USEPA Superfund Innovative Technology Evaluation (SITE) program to evaluate a chemical oxidation technology (sodium persulfate) developed at UCONN. A protocol to assess the efficacy of oxidation technologies has been used. This protocol, which consists of obtaining data from a treatability study, tested two in-situ chemical oxidation technologies that can be used on soil and groundwater at a site in Vernon, Connecticut. Based on the treatability report results and additional field data collected at the site, the design for the field implementation of the chemical oxidation remediation was completed. The results indicate that both sodium persulfate and potassium permanganate were able to effectively degrade the target VOCs (i.e., PCE, TCE and cis-DCE) in groundwater and soil-groundwater matrices. In the sodium persulfate tests (120 hrs), the extent of destruction of target VOCs was 74% for PCE, 86% for TCE and 84% for cis-DCE by Na₂S₂O₈ alone and 68% for PCE, 76% for TCE, and 69% for cis-DCE by Fe(II)-catalyzed Na₂S₂O₈. The results demonstrate the sodium persulfate's ability to degrade PCE, TCE and cis-DCE. It is expected that given sufficient dose and treatment time, a higher destruction rate of the dissolved phase contamination can be achieved. The data also indicates that the catalytic effect of the iron chelate on persulfate chemistry was much less pronounced in the soil-groundwater matrix. This indicates an interaction between the iron chelate solution and the soil, which may have resulted in a lower availability of the chelated iron for catalysis. The study showed that the remediation of the VOCs-contaminated soil and groundwater by in-situ chemical oxidation using sodium persulfate is feasible at the Roosevelt Mills site. As a result, the USEPA SITE program will evaluate this technology at this site.     

Geochemistry of Iron and Sulfur in the Zone of Microbial Sulfate Reduction in Mine Tailings

The cycling of iron and sulfur in mine tailings depends on various chemical and microbial reactions. The present study was undertaken in order to assess the role played by populations of sulfate-reducing bacteria (SRB) on the fate of Fe and SO₄ ^2- in Cu–Zn and Au tailings. Samples were taken along a 50-cm deep profile at all sites and analyzed for SRB populations, solid-phase mineralogy and porewater geochemistry. Results indicated that the Cu–Zn tailings were highly oxidized near the surface, as shown by the very low pH, high redox potential, large concentrations of soluble Cu, Zn and sulfate in the porewaters, and the depletion of pyrite. On the other hand, Au tailings were more pH neutral, slightly anoxic, and showed low concentrations of Fe and SO₄ ^2- in the porewaters and very little pyrite oxidation. SRB populations in the Cu–Zn tailings increased with depth, just below the oxic/anoxic interface and were linked to a decline of sulfate and DOC concentrations around the same depths. However, large concentrations of dissolved Fe were also observed around the same depth intervals. Our results suggest that SRB could be involved in sulfate reduction in the Cu–Zn tailings, because the solubility of sulfate was not controlled by the precipitation of sulfate-rich minerals. However, the presence of soluble Fe in the reduced portion of the tailings was also indicative of the presence of iron reducing bacteria (IRB). These bacteria were not enumerated in the present study, but their co-occurrence with SRB has been reported in the past in similar mining environments. The decline of sulfate and the release of soluble iron into the porewaters were also paralleled by a pH increase and the generation of alkalinity. In the Au tailings, SRB populations were generally constant throughout the depth profile and could not be ascribed to sulfate reduction in the porewaters. The solubilities of sulfate and iron in these tailings were partially controlled by jarosite and Fe-oxide minerals. It is then clear that SRB populations could be recovered from various mining sites, but their activity cannot be ascertained based on microbial enumeration and geochemical data.     

掺杂过渡金属离子的纳米二氧化钛光催化氧化对氯苯酚的研究

以掺杂过渡金属离子Fe^ 的纳米Ti02为光催化剂，以高压汞灯为光源，研究了对氯苯酚在水悬浮溶液中的降解，考察了对氯苯酚的初始浓度、气相氧浓度、催化剂投加量、光强对对氯苯酚光解速率的影响。通过试验发现，光强、气相氧浓度以及催化剂投加量是影响光催化氧化反应的关键因素。采用掺杂过渡金属粒子Fe^3 的纳米TiO2为光催化剂比采用纯纳米TiO2为光催化剂对氯苯酚降解率提高了近1．4倍。     

Removal of decabromodiphenyl ether (BDE-209) by sepiolite-supported nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) synthesized using sepiolite as a supporter was used to investigate the removal kinetics and mechanisms of decabromodiphenyl ether (BDE-209). BDE-209 was rapidly removed by the prepared sepiolite-supported nZVI with a reaction rate that was 5 times greater than that of the conventionally prepared nZVI because of its high surface area and reactivity. The degradation of BDE-209 occurred in a stepwise debromination manner, which followed pseudo-first-order kinetics. The removal efficiency of BDE-209 increased with increasing dosage of sepiolite-supported nZVI particles and decreasing pH, and the efficiency decreased with increasing initial BDE-209 concentrations. The presence of tetrahydrofuran (THF) as a cosolvent at certain volume fractions in water influenced the degradation rate of sepiolite-supported nZVI. Debromination pathways of BDE-209 with sepiolite-supported nZVI were proposed based on the identified reaction intermediates, which ranged from nona- to mono-brominated diphenylethers (BDEs) under acidic conditions and nona- to penta-BDEs under alkaline conditions. Adsorption on sepiolite-supported nZVI particles also played a role in the removal of BDE-209. Our findings indicate that the particles have potential applications in removing environmental pollutants, such as halogenated organic contaminants.