纤铁矿微生物异化还原过程的动力学特征及其影响因素

基于脱色希瓦氏菌(Shewanella decolorationis S12)和纤铁矿相互作用的现象,探讨了电子供体、纤铁矿浓度及氧化还原中介体2-磺酸钠蒽醌(AQS)对其相互作用的影响.结果表明,AQS的加入使纤铁矿的微生物还原程度得到加强.反应末期,乳酸钠浓度为20mmol.L-1时,在添加AQS的10.0mmol.L-1的纤铁矿体系中,被还原解离出的Fe(Ⅱ)浓度是无AQS体系中的180.2%.纤铁矿的归一化还原速率表明,当电子供体浓度一定时,随着纤铁矿浓度的增加,纤铁矿的还原酶促反应显著减弱.米氏拟合方程表明,以不同浓度的纤铁矿为底物时,S12菌-纤铁矿相互作用过程的拟合校正R2系数分别为0.8285(添加AQS)和0.9348(未添加AQS),电子转移载体的存在及底物类型的不同均对底物饱和时的反应速度(Vmax)和米氏常数(Km)值均有一定程度的影响.在微生物还原纤铁矿过程中,氧化还原中介体AQS使得其还原程度加剧,用于ATP合成所需能量ΔE值也随之升高,S12菌和纤铁矿的还原反应达到平衡时,Gibbs自由能变化(ΔGr)达最大值.     

针铁矿的非生物还原解离特征及Slogistic模型拟合

以针铁矿为研究对象,分析了电子供体和针铁矿浓度以及氧化还原中介体AQS对针铁矿非生物还原解离作用的影响.结果表明,在没有氧化还原中介体的参与下,针铁矿的非生物还原作用十分微弱;AQS加入体系后,针铁矿的非生物还原程度在经历一定的反应时间后显著加剧,且还原过程中生成的解离态Fe(ΙΙ)含量随时间的变化趋势符合典型的Slogistic曲线特征.Slogistic拟合结果表明:一定电子供体浓度下,不同浓度针铁矿的非生物还原Slogistic模型拟合的校正R2在0.9887~0.9953之间.当针铁矿浓度维持为一恒定值时,电子供体浓度不足的情况下,针铁矿的非生物还原的Slogistic 曲线特征较弱;当电子供体浓度充足的条件下,Slogistic模型拟合的校正R2系数可高达0.9967.电子供体和针铁矿浓度以及氧化还原中介体AQS的参与对Slogistic模型拟合参数均有一定的影响.     

蒽醌类有机质对针铁矿异化还原解离特征影响

基于希瓦氏金属还原菌(Shewanella decolorationis S12)和针铁矿相互作用,讨论了蒽醌类有机质(AQS)对该针铁矿异化还原过程的调控机制.结果表明:AQS作为电子运移载体,使得还原解离态铁总量(Fetot)和可溶态铁含量(Fedis)均快速增加;不同含量的AQS加入前后,针铁矿还原平均速率得到显著上升,速率比在2.4~4.0之间,且该比值和AQS含量呈显著的线性关系,可决系数为0.9947.Fedis/Fetot比值随AQS含量升高而降低,当AQS含量由0.05 mmol·L-1增加至0.3 mmol·L-1时,Fedis/Fetot比值由0.935减小至0.705.Feads含量随AQS含量增加而增加,当体系中无AQS时,Feads含量维持在较低的水平(0.05 mmol·L-1).AQS参与下的铁异化还原过程实际上是由两个独立的子过程组成,即微生物呼吸作用驱动了AQS和还原态蒽二酚(AH2QS)的循环转变过程以及AH2QS进一步还原解离针铁矿的非生物过程.     

微生物异化还原针铁矿过程中4-硝基苯乙酮降解动力学特征及机理初探

以硝基类有机污染物为研究对象,探讨了在多相界面(矿物相/生物相)反应体系及纯生物相反应体系中4-硝基苯乙酮微生物还原动力学特征,同时对"针铁矿-微生物-4-硝基苯乙酮"相互作用机制进行了初步阐明.结果表明,2-磺酸钠蒽醌(AQS)对4-硝基苯乙酮微生物还原降解速率有显著的促进作用;不同反应体系中还原降解产物4-氨基苯乙酮含量(μmol·L-1)的对数值和反应时间(h)之间均呈典型的动力学一级增长模式(ExpGro1 Mode),ExpGro1模型拟合的校正R2系数(R2adj)在0.9699～0.9894之间.针铁矿介导下的多相界面反应体系中,4-硝基苯乙酮微生物还原过程可分为耦合的两个子过程,即针铁矿的微生物还原解离过程和吸附态Fe(Ⅱ)调控下的非生物还原过程.不同浓度的AQS以及反应体系中针铁矿的介入,导致4-硝基苯乙酮微生物还原反应所需"活化时间"存在一定程度的差异.研究进一步证实,针铁矿还原解离过程生成的吸附态活性Fe("Ι)在4-硝基苯乙酮微生物还原过程中起到了至关重要的作用.     

奥奈达希瓦氏菌MR-1还原U(VI)的特性及影响因素

探讨了在腐殖质模式物蒽醌?2?磺酸钠(AQS)存在条件下,奥奈达希瓦氏菌MR-1的还原U(VI)特性.结果表明,在厌氧环境下奥奈达希瓦氏菌以AQS为电子穿梭载体,利用电子供体高效还原U(VI).当菌体投加量为1.2×109 个时,其还原铀的效率达95.09%; AQS的浓度低于0.5mmol/L时有利于MR-1菌厌氧还原U(VI),AQS浓度的升高U(VI)的还原明显受到抑制.当U(VI)初始浓度为30.0mg/L时,分别以甲酸盐、乙酸盐和乳酸盐为电子供体,经过7d后其还原率分别达到95.37%、92.41%和95.65%.金属离子(Cu2+、Mn2+、Ca2+)、有毒有机物等对U(VI)还原产生影响.当Ca2+的浓度为2.0mmol/L时,对U(VI)的还原有微弱的促进作用,而当Cu2+和Mn2+浓度为2.0mmol/L时,则存在较强的抑制作用.奥奈达希瓦氏菌也能利用环境中甲苯、三氯乙酸、顺丁烯二酸等有毒物质高效还原U(VI),同时使有毒物质得到降解.扫描电子显微镜(SEM)和电子能谱(EDS)分析结果表明,奥奈达希瓦氏菌菌体中沉积了铀元素.     

生物炭及其水溶组分促进水铁矿微生物还原

采用水稻秸秆在300,400和500℃热解温度下制备生物炭(BC),并从中提取生物炭水溶组分(DBC),结合微生物还原实验和傅里叶转换红外光谱仪(FTIR)、X射线衍射晶体衍射(XRD)、电子顺磁(EPR)等表征手段考察BC和DBC对Geobacter sulphurreducens PCA还原水铁矿的影响和作用机制.结果表明,400℃热解BC可使微生物异化铁还原的速率增加12倍,还原率最高,这是由于其含有最多的醌基、羧基基团,可以作为电子穿梭体促进电子转移.BC不能作为电子供体直接向微生物或水铁矿提供电子.DBC使水铁矿的长期微生物异化铁还原程度和初始还原速率分别增加了10倍和2倍以上.500℃热解DBC可以充当电子供体或者电子穿梭体,促进水铁矿的微生物还原,但是不能直接化学还原水铁矿.     

蒽醌类有机质介导水铁矿电化学还原的动力学

以水铁矿为实验对象，采用计时电流法研究了"电极-AQS-水铁矿"反应体系中蒽醌介导下的电化学还原动力学过程，阐明了"电极-AQS-水铁矿"三者之间相互作用的动力学特征与机制.结果表明：在超声波的协助下，同市售玻碳电极相比，发生在碳毡电极表面的电化学还原反应的灵敏性得到显著提升，且当体系施加电压为-0.7V时，AQS可以被完全还原.在最佳工作电极和实验条件下，AQS可以作为氧化还原中介体参与水铁矿的电化学还原过程.当AQS浓度从0.005mmol/L升至0.035mmol/L时，单位绝对量水铁矿的还原率从10.4%增至35%.AQS介导水铁矿电化学还原过程中的中间产物AQS_oxi浓度随时间的变化趋势符合由连串反应动力学推导出的函数模型曲线特征：随着时间t的增加，C_AQSoxi在初始某一范围内迅速增长；当时间到达某限度后，C_AQSoxi又出现了不同程度的快速下降，模型拟合的校正决定系数高达0.9990.     

铁氧化物与电子供体基质交互作用对红壤性水稻土中DDT还原脱氯影响

铁氧化物与电子供体基质交互作用对电子转移及具有脱氯功能的铁还原菌生长有重要影响,进而可能影响土壤中多氯代有机物的还原脱氯降解.本研究采用土壤厌氧培养实验,分析铁氧化物(针铁矿)和电子供体基质(正丁酸和乙醇)及其交互作用对红壤性水稻土中DDT脱氯的影响及其机制.结果表明,由于DDT脱氯降解,DDT及其降解产物与土壤形成结合态残留,厌氧培养6周后,土壤中DDT可提取态残留量仅为初始量的1.29%~2.01%.DDT厌氧脱氯降解的主要产物为DDD.在培养前期,加入正丁酸和乙醇使反应体系的pH降低Eh增加,进而不利于DDT还原脱氯降解.添加针铁矿或者同时添加针铁矿和电子供体基质均使反应体系的pH增加Eh降低,并且增加土壤中二价铁的量,从而促进DDT还原脱氯降解.正丁酸和铁氧化物对DDT还原脱氯无显著交互作用,而乙醇和铁氧化物对DDT还原脱氯具有拮抗作用.本研究结果对于制定DDT污染土壤的高效原位修复技术方案具有重要意义.     

溶解有机质对微生物异化还原铁过程中砷含量及其形态赋存规律的影响

基于典型的希瓦氏金属还原菌(Shewanella decolorationis S12)和石英砂负载铁砷(As-IOCS)的相互作用,探讨了不同来源及组分溶解有机质和生物/非生物条件下对上述作用过程的影响.结果表明,不同类型及组分溶解有机质(DOM)均能使石英砂上负载的铁砷微生物还原解离/解吸程度得到一定程度的加强.而非生物反应体系中,只有含氧化还原敏感官能团结构的蒽醌类物质(0.1 mmol·L-1AQS)对铁砷的解离/解吸作用产生明显影响.在0.1 mmol·L-AQS和有机络合物(2 mmol·L-1 EDTA)的影响下,使得石英砂上负载铁的微生物异化还原程度加强,导致As(Ⅴ)从石英砂负载铁上的解吸程度也随之得到加强;在未加菌体系中,AQS和EDTA和不同组分的DOM类似,对As(Ⅴ)从IOCS上解吸程度影响微弱.对于As(Ⅲ)来说,只有在AQS的影响下,其含量得到显著增加,这可能是作为氧化还原中介体的AQS,在厌氧的生物/非生物条件下,能促进电子在As不同形态之间的转移,使得高价态As(Ⅴ)向还原态As(Ⅲ)的还原转变更易进行.当S12菌液接种含量增加时,在污泥不同组分DOM的影响下,As(Ⅴ)的解吸程度在反应300h前得到明显加强,而As(Ⅲ)的含量在整个反应期间,均快速上升,表明菌液含量高的体系,微生物铁异化还原过程得以持续进行,同时也促进了As(Ⅴ)向As(Ⅲ)的还原转变.     

成团泛菌MFC-3的分离鉴定及其腐殖质/Fe(Ⅲ)呼吸特性研究

从地下古森林沉积物样品中富集分离到1株腐殖质/Fe(Ⅲ)还原菌MFC-3菌株,经16S rDNA基因序列分析,该菌与成团泛菌Pantoea agglomerans WAB1951的相似性为99%,确定为成团泛菌.通过序批式厌氧实验考察了MFC-3的腐殖质呼吸活性、电子利用情况以及对4种铁氧化物的还原活性.结果表明,MFC-3能够以AQDS为唯一电子受体进行厌氧胞外呼吸,可利用的电子供体有:甲酸、乳酸、丙三醇、柠檬酸、葡萄糖和蔗糖,且AQDS还原速率顺序为:蔗糖葡萄糖柠檬酸乳酸丙三醇甲酸;以葡萄糖作为电子供体时,48 h内0.3 mmol.L-1的AQDS被还原,同时4.5 mmol.L-1葡萄糖被消耗,菌数增殖近7倍,证明MFC-3能够进行腐殖质呼吸;MFC-3还能以多种Fe(Ⅲ)氧化物为电子受体进行厌氧呼吸,25 d内分别有2.5 mmol.L-1水铁矿、2.1 mmol.L-1纤铁矿、2.3 mmol.L-1针铁矿及0.8 mmol.L-1赤铁矿被还原溶解.本研究为胞外呼吸研究与应用提供1株适宜的模式菌株.     

Migration and transformation of Sb are affected by Mn(III/IV) associated with lepidocrocite originating from Fe(II) oxidation

Antimony (Sb) is a recognized priority pollutant with toxicity that is influenced by its migration and transformation processes. Oxidation of Fe(II) to Fe(III) oxides, which is a common phenomenon in the environment, is often accompanied by the formation of Mn(III/IV) and might affect the fate of Sb. In this study, incorporated Mn(III) and sorbed/precipitated Mn(III/IV) associated with lepidocrocite were prepared by adding Mn(II) during and after Fe(II) oxidation, respectively, and the effects of these Mn species on Sb fate were investigated. Our results indicated that the association of these Mn species with lepidocrocite obviously enhanced Sb(III) oxidation to Sb(V), while concomitantly inhibiting Sb sorption due to the lower sorption capacity of lepidocrocite for Sb(V) than Sb(III). Additionally, Mn oxide equivalents increased in the presence of Sb, indicating that Sb oxidation by Mn(III/IV) associated with lepidocrocite was a continuous recycling process in which Mn(II) released from Mn(III/IV) reduction by Sb(III) could be oxidized to Mn(III/IV) again. This recycling process was favorable for effective Sb(III) oxidation. Moreover, Sb(V) generated from Sb(III) oxidation by Mn(III/IV) enhanced Mn(II) sorption at the beginning of the process, and thus favored Mn(III/IV) formation, which could further promote Sb(III) oxidation to Sb(V). Overall, this study elucidated the effects of Mn(III/IV) associated with lepidocrocite arisen from Fe(II) oxidation on Sb migration and transformation and revealed the underlying reaction mechanisms, contributing to a better understanding of the geochemical dynamics of Sb.     

The effect of light on the Mn(II) or Fet(lll)-catalyzed oxidation of aqueous S(IV)

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不同Fe(III)对活性污泥异化铁还原及除磷影响研究

以SBBR反应器活性污泥作为铁还原菌菌种来源,采用兼性厌氧/严格厌氧恒温培养试验,投加不同Fe(III)考察各条件下的异化铁还原能力,同时比较对磷的去除效果.结果表明:2种条件下Fe(III)还原能力具有较好的一致性,依次为:Fe(OH)3>氧化铁皮>青矿>红矿,其中严格厌氧条件下较好.同时,除磷效果与其呈正相关,富集培养至7d, Fe(OH)3及氧化铁皮体系出水磷浓度均达到2mg/L以下,之后继续降低,最终达到0.5mg/L以下.结合异化铁还原除磷机理,可以证明,不同Fe(III)表面吸附作用对TP的去除贡献较小,其主要作用为铁还原菌驱动下的化学沉淀去除.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

重金属元素BCR提取法及在太湖沉积物研究中的应用

采用BCR提取法,HCl-HNO3-HF消化法和ICP-AES仪器测定了西太湖沉积岩芯中Cu,Fe,Mn,Ni,Pb和Zn 6种重金属元素不同形态的质量分数.结果表明:采用BCR方法对太湖沉积物重金属元素形态进行提取,提取结果具有较高的精度和稳定性;受元素地球化学性质及沉积物理化性质的影响,Cu,Fe,Ni和Zn以残渣态为主;Mn以可交换态及碳酸盐结合态为主;Pb的有机物及硫化物结合态,Fe/Mn氧化物结合态以及残渣态的质量分数基本一致;重金属元素Fe/Mn氧化物结合态的质量分数与可还原态Mn质量分数有较好的正相关性,有机物及硫化物结合态的质量分数与有机质质量分数相关性较好.      

USY负载MnOx催崔化剂NH3选择还原NOx性能的研究

采用USY分子筛为载体制备MnOx催化剂,考察了制备方法、前躯体、焙烧温度、催化组分负载量不同的情况下NH3选择催化还原NOx的能力,同时考察了添加Fe和Ce对Mn/USY催化剂脱硝性能的影响.结果表明,采用浸渍法负载10％的醋酸锰并在500℃下焙烧所制得的催化剂,在80～320℃范围内具有很高的催化活性;Fe、Ce的...     

Lead adsorption capacities of different components in natural surface coatings

Pb adsorption capacities of Fe oxide, Mn oxide and organic materials in natural surface coatings (biofilms and associated minerals) collected in three lakes, two ponds and a river in Jilin Province, China and Cayuga Lake in US were studied. A novel extraction technique was employed to remove one or more component(s) from the surface coatings. Pb adsorption to surface coatings before and after extraction was performed to determine the adsorptive properties of the extracted component(s). The statistical analysis of observed Pb adsorption was carried out using nonlinear least squares fitting (NLSF) to estimate the Pb adsorption capacity of each component of surface coatings. For each body of water, the estimated Pb adsorption capacity of Mn oxide( mol Pb/mol Mn) was significantly higher than that of Fe oxide( mol Pb/ mol Fe). The value of estimated adsorption capacities of organic materials with the unit mol Pb per kg COD was similar to or less than that of Fe oxides with the unit mol Pb per mol Fe. Comparison of components of surface coatings in different waters showed that the estimated Pb adsorption capacities of components in surface coatings developed in different natural waters were different,especially for Mn oxides.     

Dissimilatory Fe(III) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe(OH)3 as the sole electron acceptor. The results showed significant differences in Fe(Ⅲ) reduction among the three paddy soil solutions and suhstrate types. Bacteria from the Sichuan paddy soil responded quickly to substrate supply and showed higher Fe(Ⅲ) reducing activity than the other two soil types. Bacteria in the Jiangxi paddy soil culture solution could not use propionate as a source of electrons for Fe(Ⅲ) reduction. Similarly, bacteria in the Jilin paddy soil culture could not use succinate effectively. Pyruvate was readily used by cultures from all three paddy soil solutions, thus indicating that there were some similarities in substrate utilization by bacteria for Fe(Ⅲ) reduction. The use of glucose and citrate as substrate for dissimilatory Fe(Ⅲ) reduction indicates important ecological implications for this type of anoxic respiration.