Though the geology of earth's rare geothermal environments and their associated microbial communities are intensely studied, less scientific attention has focused on their potential effects through the plant-herbivore-carnivore trophic chain. The west-central portion of Yellowstone National Park contains a 2000-km² volcanic caldera with 2- to 60-million-year-old, predominantly rhyolitic, rocks that produce relatively infertile soils. The caldera area contains one of the largest concentrations of active geothermal features in the world, including thousands of geysers, fumaroles, hot springs, and mud pots. In many other chapters of this book, we address the ecological impacts of this unique geology to the ecology of the large mammals that live within the caldera, primarily through the effects of geothermal heat on snow pack. In this chapter, we explore the unique geochemistry of the geothermal environments and the consequences of this geochemistry to elk and perhaps other herbivores that reside within the caldera. These studies were prompted by behavioral and demographic observations of elk during the initial years of our studies that we could not explain and, in turn, led us to formulate hypotheses about potential geochemical influences on elk ecology. Specifically, we contrast the concentrations of fluoride (F) and silica (SiO₂) found in the Madison headwaters area with areas on Yellowstone's northern range located approximately 50 km to the northwest, where geothermal features are rare or absent. We then trace the consequences of geochemical differences through abiotic and biotic linkages in the ecosystem.