ALBERT

Description: The dataset contains boron (B) concentrations and isotope ratios of hydrothermal vent fluids and volcanic rocks from different vent fields within the Manus Basin, Papua New Guinea, and Nifonea volcano, New Hebrides back-arc. The fluids from these settings show a range of salinities, gas contents, acidities, and host rock compositions; many of them are influenced by phase separation and by addition of magmatic volatiles (both CO2 and SO2). Previous studies of hydrothermal vents in arc/back-arc settings suggest that B contents and isotopic composition of vent fluids are controlled by interactions between seawater, basement and sediments, and propose that phase separation and magmatic fluids play only a subordinate role. In our study, we demonstrate that vent fluids with minor magmatic input indeed reflect the interaction between seawater and oceanic crust. In contrast, the low-salinity Nifonea fluids and some of the acid-sulfate fluids from the Manus Basin have higher B contents as expected, whereas other volatile-rich fluids from the Manus Basin show B depletions. The lack of correlation between B contents and the intensity of magmatic fluid influx (CO2 and SO2) may indicate that magma degassing is not responsible for the B enrichments or depletions in these vent fluids. B enrichments might be related to preferential partitioning of B into the vapour phase during phase separation under PT-conditions well above the two-phase curve and critical line (i.e. T 〉〉 Tcritical, P 〉〉 Pcritical). However, this cannot explain the low B concentrations in the vapour-rich vent fluids from the Manus Basin and the low B isotope ratios in the Nifonea fluids. Instead, we propose that B concentrations and isotope ratios in submarine vent fluids largely depend on the residence and reaction time of the vent fluid in the subsurface. In general, all vent fluids are still influenced by water-rock interaction during hydrothermal circulation. However, vent fluids with short residence times define a trend towards lower B concentrations and isotope ratios, which can be explained by mixing between hydrothermal and magmatic fluid, which is similar to the composition of the host rock. In contrast, the B signature of the magmatic fluid can be overprinted due to preferential mobilization of B from the oceanic crust into vapour-rich fluids at longer reaction times. Thus, B may provide a tool for estimating the extent of B leaching and hence hydrothermal alteration in the subseafloor.

Description: Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = 〈0.02 µg/g; d11BOlivine -14 per mil; [Li] = 1.7 µg/g; d7LiOlivine = +5.3 per mil) with seawater-like fluids (75 ml, 3.2 wt.% NaCl) adjusted with respect to their Li (0.2, 0.5 µg/ml; and d7LiFluid +55 per mil) and B (~10 µg/ml and d11BFluid -0.3 per mil) characteristics. At 200 °C a reaction turnover of about 70% and a serpentinization mineral assemblage matching equilibrium thermodynamic computational results (EQ3/6) developed after 224 days runtime. Characterization of concomitant fluid samples indicated a distinct B incorporation into solid phases ([B]final_200 °C = 55.61 µg/g; DS/FB200 °C = 13.42) and a preferential uptake of the lighter 10B isotope (Delta11BS-F = -3.46 per mil). Despite a low reaction turnover at 100 °C (〈12%), considerable amounts of B were again incorporated into solid phases ([B]final_100 °C = 25.33 µg/g; DS/FB100 °C = 24.2) with even a larger isotope fractionation factor (Delta11BS-F = -9.97? per mil. While magnitude of isotope fraction appears anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 µg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower d7LiF of +38.62 per mil. Newly formed serpentine minerals (d7LiS = +30.58 per mil) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 µg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes.

Description: The Central Andes of South America hosts the largest known lithium anomalies in a restricted area, but the primary lithium sources of the salar deposits and the mobilization process of lithium are still a matter of speculation. Chemical weathering at or near the surface and leaching in hydrothermal systems of the active magmatic arc are considered as the two main mechanisms of Li extraction from the source rock. The lithium and strontium isotope composition of typical salar deposits offer insights into the processes on how Li brine deposits in Andean evaporites are formed. Data from the Salar de Pozuelos indicate surface near chemical weathering in a cold and dry climate as the dominant mobilization process of Li, with evaporation being responsible for the enrichment. The Cenozoic ignimbrites are the favourite source rock for the Li, with subordinate additions from the Palaeozoic basement. The identification of the source rocks is supported by radiogenic Nd and Pb, and stable B isotope data from salar deposits. A comparison with other Li brine and salt deposits in the Altiplano-Puna Plateau and its western foothills places the Salar de Pozuelos as an endmember of Li solubilisation by surface near chemical weathering with only minor hydrothermal mobilization of Li.

Description: Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.