Thi Hao Bui

Diazonium-induced anchoring process: an application to improve the monovalent selectivity of cation exchange membranes

An efficient and one-step chemical process (diazonium-induced anchoring process) to graft covalently a thin polyaniline-like layer on the surface of the Selemion CMV commercial cation exchange membrane is reported. SEM, IR and XPS techniques were used to characterize the obtained polymer film. The ability of such a surface modification layer to improve the membrane selectivity for hydrogen ions was confirmed by means of electrodialysis test. In contact with a mixed solution of sulfuric acid and metallic divalent salts, the protonation reaction of the polyaniline-like layer creates positive charges, thus leading to an electrical repulsion barrier which may reduce the penetration of divalent cations with respect to hydrogen ions. The ion exchange capacity, the membrane conductivity as well as the competitive transport of nickel and proton ions inside the modified membrane are discussed in detail in comparison with those of the bare membrane.

Bacterial sulfur disproportionation constrains timing of Neoproterozoic oxygenation

Various geochemical records suggest that atmospheric O 2 increased in the Ediacaran (635–541 Ma), broadly coincident with the emergence and diversification of large animals and increasing marine ecosystem complexity. Furthermore, geochemical proxies indicate that seawater sulfate levels rose at this time too, which has been hypothesized to reflect increased sulfide oxidation in marine sediments caused by sediment mixing of the newly evolved macrofauna. However, the exact timing of oxygenation is not yet understood, and there are claims for significant oxygenation prior to the Ediacaran. Furthermore, recent evidence suggests that physical mixing of sediments did not become important until the late Silurian. Here we report a multiple sulfur isotope record from a ca. 835–630 Ma succession from Svalbard, further supported by data from Proterozoic strata in Canada, Australia, Russia, and the United States, in order to investigate the timing of oxygenation. We present isotopic evidence for onset of globally significant bacterial sulfur disproportionation and reoxidative sulfur cycling following the 635 Ma Marinoan glaciation. Widespread sulfide oxidation helps to explain the observed first-order increase in seawater sulfate concentration from the earliest Ediacaran to the Precambrian-Cambrian boundary by reducing the amount of sulfur buried as pyrite. Expansion of reoxidative sulfur cycling to a global scale also indicates increasing environmental O 2 levels. Thus, our data suggest that increasing atmospheric O 2 levels may have played a role in the emergence of the Ediacaran macrofauna and increasing marine ecosystem complexity.

Anomalous sulfur isotopes trace volatile pathways in magmatic arcs

The cycle of sulfur, an important volatile in Earth9s crust, is the driver of many significant processes such as biological evolution, climate change, and the formation of ore deposits. This study investigates the ancient cycle of volatiles by tracing the indelible signal of anomalous sulfur isotopes, expressed as Δ 33 S ≠ 0, to illuminate the pathway of sulfur recycling through magmatic arcs. We selected the ca. 2.0 Ga Glenburgh gold deposit in the Glenburgh magmatic arc of Western Australia as a natural laboratory for this study. High-precision multiple sulfur isotope analyses of samples from the Glenburgh gold deposit and surrounding granitoid rocks yield the largest known sulfur isotope anomalies (Δ 33 S up to +0.82‰) in rocks <2.33 Ga globally. These data indicate that sulfur, and possibly gold, originated from multiple geochemical reservoirs in sedimentary rocks subducted beneath the magmatic arc, one of which is >2.33 Ga. Multiple sulfur isotope data are able to clarify a process that is cryptic to most other currently available data sets, showing that the cycling of volatiles and metals in arc settings occurs on very large scales, from the atmosphere-hydrosphere through to the lithosphere during crustal generation.

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8–3.2 billion years ago (Ga)) and Neoarchaean (2.8–2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2–2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of ~30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (−1.31 to −0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases ~3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.Oxidized sulfur, formed in photochemical reactions in an anoxic atmosphere, fuelled microbial sulfate reduction in Mesoarchaean oxygenated near-shore seas, according to sulfur and iron isotopes in pyrite.

Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks

The discovery of hydrogen-rich waters preserved below the Earths surface in Precambrian rocks worldwide expands our understanding of the habitability of the terrestrial subsurface. Many deep microbial ecosystems in these waters survive by coupling hydrogen oxidation to sulfate reduction. Hydrogen originates from water–rock reactions including serpentinization and radiolytic decomposition of water induced by decay of radioactive elements in the host rocks. The origin of dissolved sulfate, however, remains unknown. Here we report, from anoxic saline fracture waters ∼2.4 km below surface in the Canadian Shield, a sulfur mass-independent fractionation signal in dissolved sulfate. We demonstrate that this sulfate most likely originates from oxidation of sulfide minerals in the Archaean host rocks through the action of dissolved oxidants (for example, HO· and H2O2) themselves derived from radiolysis of water, thereby providing a coherent long-term mechanism capable of supplying both an essential electron donor (H2) and a complementary acceptor (sulfate) for the deep biosphere.

Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today1. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆17O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆17O values (down to −0.88‰) observed in sulfates, except for those from the terminal Cryogenian period2. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO2 and O2 and the photosynthetic O2 flux at this time3. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO2 (2–30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O2 was between 0.1–1% or 1–10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean4–6 and Phanerozoic primary production7, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O2 over geologic time8.Triple oxygen isotope measurements of 1.4-billion-year-old sedimentary sulfates reveal a unique mid-Proterozoic atmosphere and demonstrate that gross primary productivity in the mid-Proterozoic was between 6% and 41% of pre-anthropogenic levels.

Atmospheric sulfur is recycled to the crystalline continental crust during supercontinent formation

The sulfur cycle across the lithosphere and the role of this volatile element in the metasomatism of the mantle at ancient cratonic boundaries are poorly constrained. We address these knowledge gaps by tracking the journey of sulfur in the assembly of a Proterozoic supercontinent using mass independent isotope fractionation (MIF-S) as an indelible tracer. MIF-S is a signature that was imparted to supracrustal sulfur reservoirs before the ~2.4 Ga Great Oxidation Event. The spatial representation of multiple sulfur isotope data indicates that successive Proterozoic granitoid suites preserve Δ33S up to +0.8‰ in areas adjacent to Archean cratons. These results indicate that suturing of cratons began with devolatilisation of slab-derived sediments deep in the lithosphere. This process transferred atmospheric sulfur to a mantle source reservoir, which was tapped intermittently for over 300 million years of magmatism. Our work tracks pathways and storage of sulfur in the lithosphere at craton margins.The long-term evolution of the sulfur budget in the lithosphere is poorly constrained. Here, using mass independent isotope fractionation as an indelible tracer, the authors track the pathway of sulfur from the Earth’s surface to punctuated episodes of granitoid magmatism during collisional orogenesis.