Using stable isotope fractionation factors to identify Cr(VI) reduction pathways: Metal-mineral-microbe interactions.

Microbes interact with metals and minerals in the environment altering their physical and chemical states, whilst in turn metals and minerals impact on microbial growth, activity and survival. The interactions between bacteria and dissolved chromium in the presence of iron minerals, and their impact on Cr isotope variations, were investigated. Cr(VI) reduction experiments were conducted with two bacteria, Pseudomonas fluorescens LB 300 and Shewanella oneidensis MR-1, in the presence of two iron oxide minerals, goethite and hematite. Both minerals were found to inhibit the rates of Cr(VI) reduction by Pseudomonas, but accelerated those of Shewanella. The Cr isotopic fractionation factors generated by Shewanella were independent of the presence of the minerals (ε = -2.3‰). For Pseudomonas, the ε value was the same in both the presence and absence of goethite (-3.3‰); although, it was much higher (ε = -4.3‰) in the presence of hematite. The presence of aqueous Fe(III) in solution had no detectable impact on either bacterial Cr reduction rates nor isotopic fractionation factors. The presence of aqueous Fe(II) induced rapid abiotic reduction of Cr(VI). The different effects that the presence of Fe minerals had on the Cr fractionation factors and reduction rates of the different bacterial species may be attributed to the way each bacteria attached to the minerals and their different reduction pathways. SEM images confirmed that Pseudomonas cells were much more tightly packed on the mineral surfaces than were Shewanella. The images also confirmed that Shewanella oneidensis MR-1 produced nanowires. The results suggest that the dominant Cr(VI) reduction pathway for Pseudomonas fluorescens LB 300 may have been through membrane-bound enzymes, whilst for Shewanella oneidensis MR-1 it was probably via extracellular electron transfer. Since different minerals impact differentially on bacterial Cr(VI) reduction and isotope fractionation, variations of mineralogies and the associated changes of bacterial communities should be taken into consideration when using Cr isotopes to quantify Cr redox behaviour in the environment.