This study aims to explore the extent and controls of silicon isotope fractionation in hot spring systems of the Geysir geothermal area (Iceland), a setting where sinter deposits are actively formed. The δ30Si values of dissolved silica measured in the spring water and sampling sites along outflowing streams, covering a temperature range between 20 and 100 °C, were relatively constant around +0.2‰, whereas the δ30Si signatures of associated opaline sinters from the streambeds were between −0.1‰ and −4.0‰, becoming progressively more negative in the downstream parts of the aprons. Here, the deposited sinters represent some of the most 30Si depleted abiotically produced terrestrial materials documented to date. Compared to the data reported for Icelandic basalts, considered to be the source of the silicon, the δ30Si values of the fluids and sinter deposits are higher and lower, respectively.
The resulting values for apparent solid–water isotope fractionation (Δ30Sisolid–water) decreased with decreasing temperature from ca. −0.7‰ at ∼80 °C to −3.7‰ at ∼20 °C, locally down to −4.4‰. This temperature relationship was reproducible in each of the investigated hot spring systems and is qualitatively consistent with recent findings in laboratory experiments on kinetic fractionation for a flowing fluid. However, the apparent fractionation magnitudes observed in the field are ca. −2‰ more negative and thus significantly larger. We infer that solid–water silicon isotope fractionation during deposition of amorphous silica from a flowing fluid correlates inversely with temperature, but is essentially a function of the precipitation rate, such that the fractionation factor decreases with increasing rate. As an important corollary, the effective fractionation behavior during precipitation of silica from saturated solutions is a system-dependent feature, which should be taken into account when using silicon isotopes for paleo-environmental reconstructions.