Zhang Huiqin, Li Yan, Wang Xin, Lu Anhuai, Ding Hongrui, Zeng Cuiping, Wang Xiao, Wu Xiaolei, Nie Yong, Wang Changqiu
The Key Laboratory of Orogenic Belts and Crustal Evolution, School of Earth and Space Sciences, Peking University, Beijing, 100871 People's Republic of China.
Department of Energy and Resources Engineering, College of Engineering, Peking University, Beijing, 100871 People's Republic of China.
Geochem Trans. 2015 Aug 8;16:11. doi: 10.1186/s12932-015-0026-0. eCollection 2015.
Mn oxides occur in a wide variety of geological settings and exert considerable influences on the components and chemical behaviors of sediments and soils. Microbial reduction of Mn oxides is an important process found in many different environments including marine and freshwater sediments, lakes, anoxic basins, as well as oxic-anoxic transition zone of ocean. Although the pathway of Mn anaerobic reduction by two model bacteria, Geobacter and Shewanella, has been intensively studied, Mn bio-reduction is still the least well-explored process in nature. Particularly, reduction of Mn oxides by other bacteria and in the presence of O2 has been fewly reported in recent publishes.
A series of experiments were conducted to understand the capability of Dietzia DQ12-45-1b in bioreduction of birnessite. In anaerobic systems, Mn reduction rate reached as high as 93% within 4 weeks when inoculated with 1.0 × 10(10) cells/mL Dietzia DQ12-45-1b strains. Addition of AQDS enhanced Mn reduction rate from 53 to 91%. The anaerobic reduction of Mn was not coupled by any increase in bacterial protein concentration, and the reduction rate in the stable stage of day 2-14 was found to be in good proportion to the protein concentration. The anaerobic reduction of birnessite released Mn(II) either into the medium or adsorbed on the mineral or bacteria surface and resulted in the dissolution of birnessite as indicated by XRD, SEM and XANES. Under aerobic condition, the reduction rate was only 37% with a cell concentration of 1.0 × 10(10) cells/mL, much lower than that in parallel anaerobic treatment. Bacterial growth under aerobic condition was indicated by time-course increase of protein and pH. In contrast to anaerobic experiments, addition of AQDS decreased Mn reduction rate from 25 to 6%. The reduced Mn(II) combined with carbon dioxide produced by acetate metabolism, as well as an alkaline pH environment given by cell growth, finally resulted in the formation of Mn(II)-bearing carbonate (kutnohorite), which was verified by XRD and XANES results. The system with the highest cell concentration of 1.0 × 10(10) cells/mL gave rise to the most amount of kutnohorite, while concentration of Mn(II) produced with cell concentration of 6.2 × 10(8) cells/mL was too low to thermodynamically favor the formation of kutnohorite but result in the formation of aragonite instead.
Dietzia DQ12-45-1b was able to anaerobically and aerobically reduce birnessite. The rate and extent of Mn(IV) reduction depend on cell concentration, addition of AQDS or not, and presence of O2 or not. Meanwhile, Mn(IV) bioreduction extent and suspension conditions determined the insoluble mineral products.
锰氧化物存在于多种地质环境中,对沉积物和土壤的成分及化学行为有相当大的影响。锰氧化物的微生物还原是在许多不同环境中发现的一个重要过程,包括海洋和淡水沉积物、湖泊、缺氧盆地以及海洋的有氧 - 缺氧过渡带。尽管已对两种模式细菌地杆菌属(Geobacter)和希瓦氏菌属(Shewanella)进行了深入研究,但锰的生物还原仍是自然界中研究最少的过程。特别是,近期文献中很少报道其他细菌在有氧条件下对锰氧化物的还原。
进行了一系列实验以了解Dietzia DQ12 - 45 - 1b对水钠锰矿的生物还原能力。在厌氧系统中,接种浓度为1.0×10(10) 个细胞/毫升的Dietzia DQ12 - 45 - 1b菌株时,4周内锰还原率高达93%。添加蒽醌 - 2,6 - 二磺酸钠(AQDS)使锰还原率从53%提高到91%。锰的厌氧还原与细菌蛋白质浓度的任何增加均无关联,且在第2 - 14天的稳定阶段,还原率与蛋白质浓度成正比。水钠锰矿的厌氧还原将二价锰(Mn(II))释放到培养基中,或吸附在矿物或细菌表面,X射线衍射(XRD)、扫描电子显微镜(SEM)和X射线吸收近边结构(XANES)表明这导致了水钠锰矿的溶解。在有氧条件下,细胞浓度为1.0×10(10) 个细胞/毫升时,还原率仅为37%,远低于平行厌氧处理。蛋白质和pH值随时间的增加表明了有氧条件下细菌的生长。与厌氧实验相反,添加AQDS使锰还原率从25%降至6%。还原的二价锰(Mn(II))与乙酸代谢产生的二氧化碳以及细胞生长产生的碱性pH环境相结合,最终导致形成含锰(II)的碳酸盐(菱锰矿),XRD和XANES结果证实了这一点。细胞浓度最高为1.0×10(10) 个细胞/毫升的系统产生的菱锰矿量最多,而细胞浓度为6.2×10(8) 个细胞/毫升时产生的二价锰(Mn(II))浓度过低,无法在热力学上促进菱锰矿的形成,反而导致形成文石。
Dietzia DQ12 - 45 - 1b能够在厌氧和有氧条件下还原水钠锰矿。四价锰(Mn(IV))的还原速率和程度取决于细胞浓度、是否添加AQDS以及是否存在氧气。同时,四价锰(Mn(IV))的生物还原程度和悬浮条件决定了不溶性矿物产物。