Mercury isotope fractionation during liquid-vapor evaporation experiments

Liquid-vapor mercury isotope fractionation was investigated under equilibrium and dynamic conditions. Equilibrium evaporation experiments were performed in a closed glass system under atmospheric pressure between 0 and 22 °C, where vapor above the liquid was sampled at chemical equilibrium. Dynamic evaporation experiments were conducted in a closed glass system under 10⁻⁵ bar vacuum conditions varying (1) the fraction of liquid Hg evaporated at 22 °C and (2) the temperature of evaporation (22-100 °C). Both, residual liquid and condensed vapor fractions were analyzed using stannous chloride CV-MC-ICP-MS.Equilibrium evaporation showed a constant liquid-vapor fractionation factor (α_202/198) of 1.00086 ± 0.00022 (2SD, n = 6) within the 0-22 °C range. The 22 °C dynamic evaporations experiments displayed Rayleigh distillation fractionation behavior with liquid-vapor α_202/198 = 1.0067 ± 0.0011 (2SD), calculated from both residual and condensed vapor fractions. Our results confirm historical data (1920s) from Brönsted, Mulliken and coworkers on mercury isotopes separation using evaporation experiments, for which recalculated δ²⁰²Hg′ showed a liquid-vapor α_202/198 of 1.0076 ± 0.0017 (2SD). This liquid-vapor α_202/198 is significantly different from the expected kinetic α_202/198 value ((202/198)^0.5 = 1.0101). A conceptual evaporation model of back condensation fluxes within a thin layer at the liquid-vapor interface was used to explain this discrepancy. The δ²⁰²Hg′ of condensed vapor fractions in the 22-100 °C temperature range experiments showed a negative linear relationship with 10⁶/T², explained by increasing rates of exchange within the layer with the increase in temperature.Evaporation experiments also resulted in non-mass-dependent fractionation (NMF) of odd ¹⁹⁹Hg and ²⁰¹Hg isotopes, expressed as Δ¹⁹⁹Hg′ and Δ²⁰¹Hg′, the deviation in ‰ from the mass fractionation relationship with even isotopes. Liquid-vapor equilibrium yielded Δ¹⁹⁹Hg′/Δ²⁰¹Hg′ relationship of 2.0 ± 0.6 (2SE), which is statistically not different from the one predicted for the nuclear field shift effect (Δ¹⁹⁹Hg/Δ²⁰¹Hg ≈ 2.47). On the other hand, evaporation under dynamic conditions at 22 °C led to negative anomalies in the residual liquid fractions that are balanced by positive anomalies in condensed vapors with lower Δ¹⁹⁹Hg′/Δ²⁰¹Hg′ ratios of 1.2 ± 0.4 (2SD). This suggests that either magnetic isotope effects may have occurred without radical chemistry or an unknown NMF process on odd isotopes operated during liquid mercury evaporation.     

The Cretaceous iron belt of northern Chile: role of oceanic plates,a superplume event,and a major shear zone

The Cretaceous constitutes a turning point in the tectonic, magmatic, and metallogenic history of Chile. The geological evidence indicates that a major change occurred in late Neocomian time when superplume emplacement (Mid-Pacific Superplume) and plate reorganization processes took place in the Pacific. The superplume event resulted in a major ridge-push force resulting in increased coupling between the subducting and overriding plates. This completely changed the tectonic setting of Chile ending the Early Cretaceous extensional period (aborted rifting in the back-arc basin), and increasing stress at a crustal scale. As a consequence, overpressurized dioritic magmas were pushed up mainly along the best possible structural path in northern Chile, i.e., the Atacama Fault Zone, eventually forming a +500-km-long belt of Kiruna-type iron deposits with reserves of ~2,000 Mt (60% Fe), a unique case in Chile's geological history.     

Priapulid worms from the Cambrian of China shed light on reproduction in early animals

In the recent years, exceptional fossil sites have revealed astonishing details on the anatomy, lifestyles and behaviour of Cambrian animals but surprisingly, very little is known about one of their most vital features, reproduction. We describe here in situ eggs (clusters of 3 to 30 oocytes) in the tube-dwelling priapulid worm Paraselkirkia sinica from the Cambrian Stage 3 Xiaoshiba Lagerstätte (ca. 514 Ma, South China). These oocytes were accommodated within paired tubular ovaries located in the posterior half of the primary body cavity as in modern meiobenthic priapulid worms, thus indicating that the general organization of female tubular gonads in priapulid worms has remained virtually unchanged for half a billion years. Our findings provide for the first time, key information on the reproductive organs and strategies of early ecdysozoans, a huge animal clade that dominated Cambrian marine ecosystems and accounts for a large part of today's biodiversity (e.g. arthropods). Moreover, we also emphasize the critical role of ecology on the reproductive strategies and lifestyles of both modern and Cambrian worms.