Lisa E. Mayhew

Microscale imaging and identification of Fe speciation and distribution during fluid-mineral reactions under highly reducing conditions.

The oxidation state, speciation, and distribution of Fe are critical determinants of Fe reactivity in natural and engineered environments. However, it is challenging to follow dynamic changes in Fe speciation in environmental systems during progressive fluid-mineral interactions. Two common geological and aquifer materials-basalt and Fe(III) oxides-were incubated with saline fluids at 55 °C under highly reducing conditions maintained by the presence of Fe(0). We tracked changes in Fe speciation after 48 h (incipient water-rock reaction) and 10 months (extensive water-rock interaction) using synchrotron-radiation μXRF maps collected at multiple energies (ME) within the Fe K-edge. Immediate PCA analysis of the ME maps was used to optimize μXANES analyses; in turn, refitting the ME maps with end-member XANES spectra enabled us to detect and spatially resolve the entire variety of Fe-phases present in the system. After 48 h, we successfully identified and mapped the major Fe-bearing components of our samples (Fe(III) oxides, basalt, and rare olivine), as well as small quantities of incipient brucite associated with olivine. After 10 months, the Fe(III)-oxides remained stable in the presence of Fe(0), whereas significant alteration of basalt to minnesotaite and chlinochlore had occurred, providing new insights into heterogeneous Fe speciation in complex geological media under highly reducing conditions.

Phylogenetic Relationships and Functional Genes: Distribution of a Gene (mnxG) Encoding a Putative Manganese-Oxidizing Enzyme in Bacillus Species

ABSTRACT Several Bacillus and Paenibacillus species were isolated from Fe and Mn oxide minerals precipitating at a deep subsurface oxic-anoxic interface at Henderson Molybdenum Mine, Empire, CO. The isolates were investigated for their Mn(II)-oxidizing potential and interrogated for possession of the mnxG gene, a gene that codes for a putative Mn(II)-oxidizing enzyme in Bacillus species. Seven of eight Bacillus species were capable of Mn(II) oxidation; however, the mnxG gene was detected in only one isolate. Using sequences of known Bacillus species both with and without amplifiable mnxG genes and Henderson Mine isolates, the 16S rRNA and mnxG gene phylogenies were compared to determine if 16S rRNA sequences could be used to predict the presence or absence of an amplifiable mnxG gene within the genomes of the isolates. We discovered a strong correspondence between 16S rRNA sequence similarity and the presence/absence of an amplifiable mnxG gene in the isolates. The data revealed a complex phylogenetic distribution of the mnxG gene in which vertical inheritance and gene loss influence the distribution of the gene among the Bacillus species included in this study. Comparisons of 16S rRNA and functional gene phylogenies can be used as a tool to aid in unraveling the history and dispersal of the mnxG gene within the Bacillus clade.

Alteration Heterogeneities in Peridotites Exhumed on the Southern Wall of the Atlantis Massif (IODP Expedition 357)

Serpentinized and metasomatized peridotites intruded by gabbros and dolerites have been drilled on the southern wall of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) during International Ocean Discovery Program (IODP) Expedition 357. They occur in seven holes from five sites making up an east-west trending, spreading-parallel profile that crosscuts this exhumed detachment footwall. Here we have taken advantage of this sampling to study heterogeneities of alteration at scales less than a kilometer. We combine textural and mineralogical observations made on 77 samples with in situ major and trace element analyses in primary and serpentine minerals to provide a conceptual model for the development of alteration heterogeneities at the Atlantis Massif. Textural sequences and mineralogical assemblages reveal a transition between an initial pervasive phase of serpentinization and subsequent serpentinization and metasomatism focused along localized pathways preferentially used by hydrothermal fluids. We propose that these localized pathways are interconnected and form 100 m- to 1 km-sized cells in the detachment footwall. This change in fluid pathway distribution is accompanied by variable trace element enrichments in the serpentine textures: deep, syn-serpentinization fluid-peridotite interactions are considered the source of Cu, Zn, As, and Sb enrichments, whereas U and Sr enrichments are interpreted as markers of later, shallower fluid-serpentinized peridotite interaction. Alteration of gabbros and dolerites emplaced in the peridotite at different lithospheric levels leads to the development of amphibole, chlorite and, or, talc-bearing textures as well as enrichments in LREE, Nb, Y, Th, Ta in the serpentine textures of the surrounding peridotites. Combining these observations, we propose a model that places the drill holes in a conceptual frame involving mafic intrusions in the peridotites and heterogeneities during progressive alteration and emplacement on the seafloor.