Thermodynamics and kinetics of sulfide oxidation by oxygen: a look at inorganically controlled reactions and biologically mediated processes in the environment.
Thermodynamics and kinetics of sulfide oxidation by oxygen: a look at inorganically controlled reactions and biologically mediated processes in the environment.
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DOI：
10.3389/fmicb.2011.00062
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发表时间：
2011
影响因子：
5.2
通讯作者：
Girguis PR
中科院分区：
文献类型：
--
作者：
Luther GW 3rd;Findlay AJ;Macdonald DJ;Owings SM;Hanson TE;Beinart RA;Girguis PR
硫化物和氧的第一电子转移步骤的热力学表明，该反应是不利的，因为需要产生不稳定的超氧化物和二硫化物自由基离子。然而，双电子转移是有利的，因为稳定的S（0）和过氧化物将形成，但接受电子的氧中的部分填充轨道阻止快速动力学。当还原的铁和/或锰被氧氧化形成氧化的金属，其又氧化硫化物时，非生物硫化物氧化动力学得到改善。生物硫氧化依赖于已经进化以克服这些动力学约束的酶来影响硫化物的快速氧化。在这里，我们回顾了现有的热力学和动力学数据的H2S和HS·以及O2，活性氧物种，硝酸盐，亚硝酸盐和NOx物种。我们还提出了新的非生物硫化物氧化的动力学数据与微量金属清洁溶液中的氧，限制非生物速率的硫化物氧化在无金属溶液中，并同意与动力学和热力学计算。此外，我们目前的实验数据，让洞察率的chemolithotrophic和cathetotrophic硫化物氧化在环境中。我们表明，无论是厌氧自养和好氧化能自养硫化物氧化率是三个或更多的数量级高于非生物率表明，在大多数环境中，生物硫化物氧化率将远远超过非生物率由于热力学和动力学的限制，在第一节的文件。这些数据重塑了我们对环境中硫化物氧化的生物和非生物贡献的思考。
The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment.
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DOI：
10.1016/j.dsr.2008.02.001
发表时间：
2008-05-01
影响因子：
2.4
作者：
Henry, Michael S.;Childress, James J.;Figueroa, Dijanna
通讯作者：
Figueroa, Dijanna
影响因子：
2.8
作者：
Baumgartner, LK;Reid, RP;Visscher, PT
通讯作者：
Visscher, PT
影响因子：
4.5
作者：
Lin, Xueju;Scranton, Mary I.;Taylor, Gordon T.
通讯作者：
Taylor, Gordon T.
影响因子：
3
作者：
Luther, George W., III;Glazer, Brian T.;Brendel, Paul J.
通讯作者：
Brendel, Paul J.
影响因子：
5
作者：
Clement, Brian G.;Luther, George W., III;Tebo, Bradley M.
通讯作者：
Tebo, Bradley M.