The rare earth element geochemistry of acid-sulphate and acid-sulphate-chloride geothermal systems from Yellowstone National Park, Wyoming, USA
Rare earth element (REE) concentrations have been determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in acid-sulphate and acid-sulphate-chloride waters and the associated sinters and volcanic rocks from the Yellowstone National Park (YNP), Wyoming, USA, geothermal system. REE concentrations in the volcanic rocks range from 222 to 347 ppm; their chondite-normalised REE patterns are typical of upper continental crust, with LREE > HREE and negative Eu anomalies. Total REE concentrations in the fluids range from 3 to 1133 nmol kg -1 (≥ 162 ppm), and ΣREE concentrations in sinter are ≥ 181 ppm. REE abundances and patterns in drill core material from YNP indicate some REE mobility. Normalisation of REE concentrations in altered Lava Creek Tuff (LCT) from Y-12 drill core to REE concentrations in fresh LCT indicate that the REE overall have been depleted with the exception of Eu, which has been decoupled from the REE series and concentrated in the altered rocks. Relative to the host rocks the REE patterns of the fluids are variably depleted in HREEs and LREEs, and usually have a pronounced positive Eu anomaly. This decoupling of Eu from the REE suite suggests that (1) Eu has been preferentially removed either from the host rock glass or from the host rock minerals, or (2) the waters are from a high temperature or reducing environment where Eu 2+ is more soluble than the trivalent REEs. Since the latter is inconsistent with production of acid-sulphate springs in a low temperature, oxidising near-surface environment, we suggest that the positive Eu anomalies in the fluids result from preferential dissolution of a Eu-rich phase in the host rock. Spatial and temporal variations in major element chemistry and pH of the springs sampled from Norris Geyser Basin and Crater Hills accompany variations in REE concentrations and patterns of individual geothermal springs. These are possibly related to changes in subsurface plumbing, which results in variations in mixing and dilution of the geothermal fluids and may have lead to changes in the extent and nature of REE complexing.