Thermochemical sulfate reduction experiments with simple amino acid and dilute concentrations of sulfate reveal significant degrees of mass-independent sulfur isotope fractionation. Enrichments of up to 13‰ for 33 S are attributed to a magnetic isotope effect (MIE) associated with the formation of thiol-disulfide, ion-radical pairs. Observed 36 S depletions in products are explained here by classical (mass-dependent) isotope effects and mixing processes. The experimental data contrasts strongly with multiple sulfur isotope trends in Archean samples, which exhibit significant 36 S anomalies. These results support an origin other than thermochemical sulfate reduction for the mass-independent signals observed for early Earth samples.anomalous | sulfur radical | thermolysis | spin-selective | hyperfine coupling S ince the report by Farquhar et al., (1) that significant deviations from the terrestrial fractionation line are observed in samples older than approximately 2.32-2.45 Ga (2, 3), considerable effort has been dedicated to identifying the origin and significance of this signal (4-10). The mass-independent signal in these ancient samples is expressed as variations in both Δ 33 S and Δ 36 S (1).* Given the observations that gas-phase reactions can produce mass-independent signals for both Δ 33 S and Δ 36 S, the first studies on this subject attributed this ancient signal to photolytic reactions in the early atmosphere. Subsequent studies also pointed out that the mass-independent reactions may also be produced by variations in the spectrum of light that drives atmospheric photolytic reactions (10-12), and other studies speculated that liquid phase reactions involving weakly bound transition states may account for these variations (7,13).In a recent report, Watanabe et al. (7) demonstrated that high temperature reduction of sulfate using alanine and glycine as organic substrates caused moderate mass-independent sulfur isotope fractionations. These authors did not identify the origin of the effect, but suggested that it was either a magnetic isotope effect (MIE) (14) or another type of isotope effect accompanying heterogeneous reactions such as adsorption of S-bearing compounds on surfaces of solids (13). Magnetic isotope effects are expressed in rare cases for isotopes with nuclear magnetic moments, like 13 C, 17 O, 29 Si, 199 Hg, 201 Hg, 73 Ge, 235 U, and 33 S (14, 15, 16). The effect is expressed when the lifetime of a radical pair is sufficient for hyperfine coupling between magnetic nuclei and unpaired electrons to influence interconversions between singlet and triplet states. This coupling in turn changes the proportion of reactive intermediates that can participate in spin-selective reactions. The 33 S nucleus has a spin of 3∕2 and a magnetic moment of 0.643 nuclear magnetons and has been implicated in at least one well-characterized example of a 33 S MIE (14,(17)(18)(19). The alternative suggestion relates to a proposal that anomalous isotope effects may be associated with heterogeneous reactions as a resu...