New experimental results of fluid-mineral reactions at hydrothermal conditions relevant to life demonstrate that key redox reactions involving iron, sulfur, and hydrogen remain at disequilibrium at 100 °C, even in a heterogeneous system and thus are energetically favorable for microbial metabolism. Predictions from geochemical models utilizing the experimental results and specific to two contrasting case studies from the East Pacific Rise were statistically characterized and correlated to the energetics of redox reactions available for intra-chimney microbial populations. In general, predictions of available energy for autotrophic metabolism are largely similar between the mature and the nascent chimneys, although important differences still exist. Metabolic processes predicted by energetics exhibit the same trends observed in the field data for the mature chimney, but overestimate the diversity observed in the nascent chimney. Several combinations of redox reaction pairs are predicted to support mixed consortia, while some combinations appear to favor more versatile microbes capable of utilizing several reactions under rapidly changing environmental conditions within chimney walls. In addition, conditions favorable to elemental sulfur reduction and methanogenesis exhibit a negative control on the diversity of microbial populations within these chimney walls, whereas H₂S oxidation, elemental sulfur oxidation and the knallgas reaction are positively correlated with both abundance and diversity of micro-organisms. Coupling field observations of both microbial diversity and geochemical heterogeneity with lab-based experimental and theoretical modeling can facilitate translation of the observed genetic diversity into physiological diversity, thus enhancing understanding of linked phenomena of microbially induced biogeochemical transformations in complex heterogeneous systems. © 2010 Blackwell Publishing Ltd.