Redox Processes in Anoxic Waters

Author(s):  
F. J. Millero

2019 ◽  
Author(s):  
Paul Pearce ◽  
Gaurav Assat ◽  
Antonella Iadecola ◽  
François Fauth ◽  
Rémi Dedryvère ◽  
...  

The recent discovery of anionic redox as a means to increase the energy density of transition metal oxide positive electrodes is now a well established approach in the Li-ion battery field. However, the science behind this new phenomenon pertaining to various Li-rich materials is still debated. Thus, it is of paramount importance to develop a robust set of analytical techniques to address this issue. Herein, we use a suite of synchrotron-based X-ray spectroscopies as well as diffraction techniques to thoroughly characterize the different redox processes taking place in a model Li-rich compound, the tridimentional hyperhoneycomb β-Li2IrO3. We clearly establish that the reversible removal of Li+ from this compound is associated to a previously described reductive coupling mechanism and the formation of the M-(O-O) and M-(O-O)* states. We further show that the respective contributions to these states determine the spectroscopic response for both Ir L3-edge X-ray absorption spectroscopy (XAS) and X-ray photoemissions spectroscopy (XPS). Although the high covalency and the robust tridimentional structure of this compound enable a high degree of reversibile delithiation, we found that pushing the limits of this charge compensation mechanism has significant effects on the local as well as average structure, leading to electrochemical instability over cycling and voltage decay. Overall, this work highlights the practical limits to which anionic redox can be exploited and sheds some light on the nature of the oxidized species formed in certain lithium-rich compounds.<br>



2019 ◽  
Author(s):  
Paul Pearce ◽  
Gaurav Assat ◽  
Antonella Iadecola ◽  
François Fauth ◽  
Rémi Dedryvère ◽  
...  

The recent discovery of anionic redox as a means to increase the energy density of transition metal oxide positive electrodes is now a well established approach in the Li-ion battery field. However, the science behind this new phenomenon pertaining to various Li-rich materials is still debated. Thus, it is of paramount importance to develop a robust set of analytical techniques to address this issue. Herein, we use a suite of synchrotron-based X-ray spectroscopies as well as diffraction techniques to thoroughly characterize the different redox processes taking place in a model Li-rich compound, the tridimentional hyperhoneycomb β-Li2IrO3. We clearly establish that the reversible removal of Li+ from this compound is associated to a previously described reductive coupling mechanism and the formation of the M-(O-O) and M-(O-O)* states. We further show that the respective contributions to these states determine the spectroscopic response for both Ir L3-edge X-ray absorption spectroscopy (XAS) and X-ray photoemissions spectroscopy (XPS). Although the high covalency and the robust tridimentional structure of this compound enable a high degree of reversibile delithiation, we found that pushing the limits of this charge compensation mechanism has significant effects on the local as well as average structure, leading to electrochemical instability over cycling and voltage decay. Overall, this work highlights the practical limits to which anionic redox can be exploited and sheds some light on the nature of the oxidized species formed in certain lithium-rich compounds.<br>



Author(s):  
Bryant C. Jurgens ◽  
Peter B. McMahon ◽  
Francis H. Chapelle ◽  
Sandra M. Eberts
Keyword(s):  


2019 ◽  
Vol 59 (6) ◽  
pp. 952-963
Author(s):  
Yu. G. Artemov ◽  
V. N. Egorov ◽  
S. B. Gulin

Based on data on the spatial distribution and fluxes of streaming (bubbling) methane within the Black Sea, the rate of dissolved methane inflow to Black Sea deep waters was assessed. Calculations showed that gas bubble streams annually replenish the methane budget in the Black Sea by 1.2 109 m3, or 0.9 Tg, which is considerably less than determined by known biogeochemical estimates of components of methane balance in the Black Sea.



1988 ◽  
Author(s):  
Alan G. MacDiarmid
Keyword(s):  


2021 ◽  
Author(s):  
Xin Sun ◽  
Claudia Frey ◽  
Emilio Garcia-Robledo ◽  
Amal Jayakumar ◽  
Bess B. Ward

AbstractNitrite is a pivotal component of the marine nitrogen cycle. The fate of nitrite determines the loss or retention of fixed nitrogen, an essential nutrient for all organisms. Loss occurs via anaerobic nitrite reduction to gases during denitrification and anammox, while retention occurs via nitrite oxidation to nitrate. Nitrite oxidation is usually represented in biogeochemical models by one kinetic parameter and one oxygen threshold, below which nitrite oxidation is set to zero. Here we find that the responses of nitrite oxidation to nitrite and oxygen concentrations vary along a redox gradient in a Pacific Ocean oxygen minimum zone, indicating niche differentiation of nitrite-oxidizing assemblages. Notably, we observe the full inhibition of nitrite oxidation by oxygen addition and nitrite oxidation coupled with nitrogen loss in the absence of oxygen consumption in samples collected from anoxic waters. Nitrite-oxidizing bacteria, including novel clades with high relative abundance in anoxic depths, were also detected in the same samples. Mechanisms corresponding to niche differentiation of nitrite-oxidizing bacteria across the redox gradient are considered. Implementing these mechanisms in biogeochemical models has a significant effect on the estimated fixed nitrogen budget.



2020 ◽  
Author(s):  
Xin Sun ◽  
Amal Jayakumar ◽  
John C. Tracey ◽  
Elizabeth Wallace ◽  
Colette L. Kelly ◽  
...  

AbstractThe ocean is a net source of N2O, a potent greenhouse gas and ozone-depleting agent. However, the removal of N2O via microbial N2O consumption is poorly constrained and rate measurements have been restricted to anoxic waters. Here we expand N2O consumption measurements from anoxic zones to the sharp oxygen gradient above them, and experimentally determine kinetic parameters in both oxic and anoxic seawater for the first time. We find that the substrate affinity, O2 tolerance, and community composition of N2O-consuming microbes in oxic waters differ from those in the underlying anoxic layers. Kinetic parameters determined here are used to model in situ N2O production and consumption rates. Estimated in situ rates differ from measured rates, confirming the necessity to consider kinetics when predicting N2O cycling. Microbes from the oxic layer consume N2O under anoxic conditions at a much faster rate than microbes from anoxic zones. These experimental results are in keeping with model results which indicate that N2O consumption likely takes place above the oxygen deficient zone (ODZ). Thus, the dynamic layer with steep O2 and N2O gradients right above the ODZ is a previously ignored potential gatekeeper of N2O and should be accounted for in the marine N2O budget.





2000 ◽  
Vol 24 (3) ◽  
pp. 179-181 ◽  
Author(s):  
Richard G. Compton ◽  
Susan J. Perkin ◽  
David P. Gamblin ◽  
James Davis ◽  
Frank Marken ◽  
...  


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