Manganese(III) dominants the mobilization of phosphorus in reducing sediments: Evidence from Aha reservoir, Southwest China.

Eutrophication has become one of the greatest threats to aquatic ecosystems. The release of phosphorus (P) from sediments exerts a critical role on eutrophication level. Both manganese (Mn) and iron (Fe), sensitive to redox conditions, own strong affinity for P. Numerous works have demonstrated that Fe was a key factor to drive P cycle in sediments. However, the role of Mn on P mobilization remains largely unexplored. Herein, the mechanism of P mobilization driven by Mn were investigated in a seasonal anoxic reservoir. Diffusive gradients in thin films (DGT) results, from both field investigations and laboratory incubations, showed P was synchronously distributed and significantly positive correlated (r2 ≥ 0.40, p < 0.01) with Mn, suggested that P cycle was associated with Mn. X-ray photoelectron spectroscopy (XPS) results showed that in the outer layers at the top 1 cm sediment pellet the contents of Mn and P occurred significantly synchronize changed, while that of Fe remains virtually unchanged when oxygen conditions changed. This demonstrated that Mn is likely to be the key factor affect P cycle. Most importantly, the relative content of Mn(III) changed the most (≈20 %) interpreted that Mn(III) is the key Mn species dominants the P mobilization. Furthermore, Dual-Beam scanning electron microscope (DB-SEM) maps clearly showed the co-enrichment of P and Mn in oxic sediments, confirmed P was mainly hosted by Mn minerals. In contrast, the random distributions and weak or negative correlations between P and Fe implied that P cycle was decouple with Fe, this resulted from that Fe was almost deposited as inert Fe fractions (>99.2 %) in reducing sediments. This study significantly expanded our knowledge on the geochemical behavior of P influenced by Mn in aquatic sediments.

Reconstructing a 300-year history of phosphorus cycle in west Chaohu Lake, China.

Anthropogenic activities could significantly increase nutrients loading, especially phosphorus (P), into aquatic systems, leading to eutrophication and disturbance of ecosystems. Detailed investigation of P cycling and its controlling factors in modern lakes could help understand mechanisms behind eutrophication, thus provide suggestions for future environmental management. Here, we investigate evolution history of P and iron (Fe) cycling over the last ∼300 years in west Chaohu Lake, a typical eutrophic lake in East China. The combination of 210Pb-137Cs dating and elemental analysis demonstrates drastic escalation of P input and organic carbon burial since 1960s, coincided with the rapid growth of human population near this region. P phase partitioning data indicate that Fe-bound P (PFe) is the predominant P pool of sediments in Chaohu Lake, which also regulates the evolving trend of reactive P (Preac). Moreover, the highest fraction of PFe is consistent with observations via P K-edge X-ray absorption near edge structure (P XANES). In addition, Fe speciation results show a principal contribution of Fe (hydr)oxides (Feox) and negligible presence of pyrite, suggesting a generally oxygenated depositional environment, where P could be preferentially sequestrated in sediments in association with Fe oxide minerals. Relatively high molar organic carbon/organic P (Corg/Porg) but low Corg/Preac ratios also support limited recycling of Preac in west Chaohu Lake. This study reveals that human activities play an important role in leading to the eutrophication of Chaohu Lake. Future environmental management could utilize the coupling of P and Fe oxides to remove P from water column.

Evaluating the abiotic synthesis potential and the stability of building blocks of life beneath an impact-induced steam atmosphere.

A prerequisite for prebiotic chemistry is the accumulation of critical building blocks of life. Some studies argue that more frequent impact events on the primitive Earth could have induced a more reducing steam atmosphere and thus favor widespread and more efficient synthesis of life building blocks. However, elevated temperature is also proposed to threaten the stability of organics and whether life building blocks could accumulate to appreciable levels in the reducing yet hot surface seawater beneath the steam atmosphere is still poorly examined. Here, we used a thermodynamic tool to examine the synthesis affinity of various life building blocks using inorganic gasses as reactants at elevated temperatures and corresponding steam pressures relevant with the steam-seawater interface. Our calculations show that although the synthesis affinity of all life building blocks decreases when temperature increases, many organics, including methane, methanol, and carboxylic acids, have positive synthesis affinity over a wide range of temperatures, implying that these species were favorable to form (>10-6 molal) in the surface seawater. However, cyanide and formaldehyde have overall negative affinities, suggesting that these critical compounds would tend to undergo hydrolysis in the surface seawaters. Most of the 18 investigated amino acids have positive affinities at temperature <220°C and their synthesis affinity increases under more alkaline conditions. Sugars, ribose, and nucleobases have overall negative synthesis affinities at the investigated range of temperatures. Synthesis affinities are shown to be sensitive to the hydrogen fugacity. Higher hydrogen fugacity (in equilibrium with FQI or IW) favors the synthesis and accumulation of nearly all the investigated compounds, except for HCN and its derivate products. In summary, our results suggest that reducing conditions induced by primitive impacts could indeed favor the synthesis/accumulation of some life building blocks, but some critical species, particularly HCN and nucleosides, were still unfavorable to accumulate to appreciable levels. Our results can provide helpful guidance for future efforts to search for or understand the stability of biomolecules on other planets like Mars and icy moons. We advocate examining craters formed by more reducing impactors to look for the preservation of prebiotic materials.