Tracing Earth's Oxygenation Events Using Metal Stable Isotopes
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摘要: 早期贫氧地球如何演化至现今富氧地球是理解地球宜居性形成与演化的关键，但重建地质历史时期地球大气与海洋氧含量仍是地球科学领域的重大挑战.金属稳定同位素的高精度测试分析为示踪地球大气与海洋氧化历史提供了新的研究手段.以Mo、U、Tl、Cr四种氧化还原敏感金属稳定同位素体系为例，详细介绍了氧化还原敏感金属稳定同位素地球化学行为及分馏机理.在此基础上，系统回顾了金属稳定同位素在研究产氧光合作用的起源、大氧化事件（Great Oxidation Event，GOE）、中元古代大气和海洋氧化还原状态、新元古代氧化事件（NOE）等重大科学问题中的研究进展.金属稳定同位素在重建地球表层圈层氧化过程具有广阔的应用前景，对认识地球宜居性的演化历史以及探索其未来发展趋势具有深远意义.Abstract: How early anoxic earth evolved to modern oxic Earth is the key to understand the formation and evolution of Earth's habitability. However, reconstructions of atmospheric and oceanic oxygen levels over Earth's history are still significant challenges. The high precision analysis of redox sensitive metal stable isotopes provides a powerful means to trace Earth's oxygenation history. In this review, it takes Mo, U, Tl, Cr isotopes as example to introduce the geochemical behaviors and fractionation mechanism of redox sensitive metal stable isotope systems. On this basis, it systematically reviews the advances of metal stable isotopes in important research issues including the onset of oxygenic photosynthesis, Great Oxidation Event (GOE), the redox state of atmosphere and ocean in the Mesoproterozoic, Neoproterozoic Oxidation Event (NOE). Metal stable isotopes have great application prospects in reconstructing the oxidation processes of Earth's surface. Furthermore, metal stable isotopes have profound significance in understanding the evolution of Earth's habitability and exploring its development in the future.
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图 1 地质历史时期大气氧气浓度变化(a)与海洋氧化还原条件变化(b)及生物演化重大事件(c)
修改自Shields-Zhou and Och（2011）；Lyons et al.（2014）；Poulton（2017）
Fig. 1. The evolution of atmospheric oxygen levels (a), marine redox states (b), as well as the major biological innovative events (c) during the geological history
图 2 氧化还原梯度带与氧化还原敏感金属稳定同位素关系概念
a.早成岩阶段普通电子受体深度分布图；b.早成岩阶段厌氧代谢产物深度分布图；c.氧化还原条件深度变化；d.在不同的氧化还原相带下氧化还原敏感金属稳定同位素响应区间；修改自Canfield and Thamdrup（2009）；Kendall（2021）；Owens（2019）
Fig. 2. Conceptual figure of the relationship between redox gradient zone and redox sensitive metal stable isotopes
图 3 现代海洋系统中Mo、U、Tl和Cr同位素循环
ΔYX=δYX-δYSW，其中Y代表氧化还原元素，X代表不同元素不同的汇；数据来源：Mo同位素（Barling et al., 2001；Siebert et al., 2003；Archer and Vance, 2008；Wasylenki et al., 2008；Nägler et al., 2011；Poulson Brucker et al., 2012；Scholz et al., 2018；Ahmad et al., 2021）；U同位素（Dunk et al., 2002；Andersen et al., 2014, 2015, 2016, 2017；Tissot et al., 2018；Zhang et al., 2020）；Tl同位素（Nielsen et al., 2005, 2006a, 2006b, 2017；Peacock and Moon, 2012；Owens et al., 2017）；Cr同位素（Jeandel and Minster, 1987；Reinhard et al., 2013；Gueguen et al., 2016；Paulukat et al., 2016；Goring-Harford et al., 2018；Wei et al., 2018b）
Fig. 3. Global cycles of Mo, U, Tl and Cr isotopes in the modern oceans.
图 4 地质历史时期沉积物Mo、U、Tl、Cr同位素组成演化图解
CZ为新生代；地壳U同位素值与现代海水U同位素平均值接近；数据来源：Mo同位素（Barling et al., 2001；Siebert et al., 2003, 2005, 2006；Arnold et al., 2004；Lehmann et al., 2007；Wille et al., 2007；Gordon et al., 2009；Voegelin et al., 2009；Duan et al., 2010；Pearce et al., 2010；Scheiderich et al., 2010；Voegelin et al., 2010；Dahl et al., 2011；Kendall et al., 2011；Neubert et al., 2011；Zhou et al., 2011；Dickson et al., 2012；Herrmann et al., 2012；Xu et al., 2012；Zhou et al., 2012；Asael et al., 2013, 2018；Wille et al., 2013；Planavsky et al., 2014a；Chen et al., 2015；Eroglu et al., 2015；Kendall et al., 2015, 2020；Kurzweil et al., 2015a, 2015b, 2016；Wen et al., 2015；Cheng et al., 2016, 2017, 2018；Romaniello et al., 2016；Diamond et al., 2018；Ossa Ossa et al., 2018a；Planavsky et al., 2018；Scholz et al., 2018；Dong et al., 2019；Ostrander et al., 2019b；Thoby et al., 2019；Zhang et al., 2019c；Gilleaudeau et al., 2020；Greaney et al., 2020；Mänd et al., 2020；Stockey et al., 2020；Ye et al., 2020；Tan et al., 2021）；U同位素（Montoya-Pino et al., 2010；Brennecka et al., 2011；Asael et al., 2013；Kendall et al., 2013, 2015；Dahl et al., 2014；Holmden et al., 2015；Noordmann et al., 2015；Wang et al., 2016, 2018；Elrick et al., 2017；Jost et al., 2017；Lau et al., 2017；Lu et al., 2017；；Song et al., 2017；Yang et al., 2017；Bartlett et al., 2018；Phan et al., 2018；Wei et al., 2018a；White et al., 2018；Zhang et al., 2018a, 2018b, 2018c, 2018d, 2019a；Dahl et al., 2019；Gilleaudeau et al., 2019；Tostevin et al., 2019；Cole et al., 2020；Mänd et al., 2020；Wang et al., 2020）；Cr同位素（Frei et al., 2009, 2011, 2013；Crowe et al., 2013；Planavsky et al., 2014b；Cole et al., 2016；Gilleaudeau et al., 2016；Rodler et al., 2016；Babechuk et al., 2017；D’Arcy et al., 2017；Canfield et al., 2018；Gilleaudeau et al., 2018；Huang et al., 2018；Wei et al., 2018a, 2021b；Colwyn et al., 2019；Toma et al., 2019）；Tl同位素（Them et al., 2018；Bowman et al., 2019；Ostrander et al., 2019a, 2020；Fan et al., 2020）
Fig. 4. Mo, U, Tl and Cr isotopic compositions of sediments through geological time
表 1 Mo、U、Tl、Cr同位素组成表示方式
Table 1. The expressions of Mo, U, Tl, Cr isotopes
同位素体系 表示方式 标样 参考文献 Mo ${{\rm{ \mathsf{ δ} }}^{98}}{\rm{Mo}}\left({\rm{‰}} \right){\rm{}} = \left({\frac{{{{({}_{\rm{}}^{98}{\rm{Mo}}/{}_{\rm{}}^{95}{\rm{Mo}})}_{{\rm{sample}}}}}}{{{{({}_{\rm{}}^{98}{\rm{Mo}}/{}_{\rm{}}^{95}{\rm{Mo}})}_{{\rm{SRM}}3134}}}} - 1} \right) \times 1{\rm{}}000 + 0.25$ NIST SRM-3134 Kendall et al.(2017) U ${{\rm{ \mathsf{ δ} }}^{238}}{\rm{U}}\left({\rm{‰}} \right){\rm{}} = \left({\frac{{{{({}_{\rm{}}^{238}{\rm{U}}/{}_{\rm{}}^{235}{\rm{U}})}_{{\rm{sample}}}}}}{{{{({}_{\rm{}}^{238}{\rm{U}}/{}_{\rm{}}^{235}{\rm{U}})}_{{\rm{CRM}}145}}}} - 1} \right) \times 1{\rm{}}000$ NIST CRM-145 Andersen et al.(2017) Tl ${\varepsilon ^{205}}{\rm{Tl}} = \left({\frac{{{{({}_{\rm{}}^{205}{\rm{Tl}}/{}_{\rm{}}^{203}{\rm{Tl}})}_{{\rm{sample}}}}}}{{{{({}_{\rm{}}^{205}{\rm{Tl}}/{}_{\rm{}}^{203}{\rm{Tl}})}_{{\rm{SRM}}997}}}} - 1} \right) \times 10{\rm{}}000$ NIST SRM-997 Nielsen et al.(2017) Cr ${{\rm{ \mathsf{ δ} }}^{53}}{\rm{Cr}}\left({\rm{‰}} \right){\rm{}} = \left({\frac{{{{({}_{\rm{}}^{53}{\rm{Cr}}/{}_{\rm{}}^{52}{\rm{Cr}})}_{{\rm{sample}}}}}}{{{{({}_{\rm{}}^{53}{\rm{Cr}}/{}_{\rm{}}^{52}{\rm{Cr}})}_{{\rm{SRM}}979}}}} - 1} \right) \times 1{\rm{}}000$ NIST SRM-979 Qin and Wang(2017) 
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