Formation mechanism of framboidal pyrite and its theory inversion of paleo-redox conditions
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摘要:
研究目的 草莓状黄铁矿广泛存在于现代沉积物和沉积岩中，其成因机制总体上分为有机成因和无机成因两种，尽管两种机制均有理论与实验的支撑，但尚未建立一种具有普遍意义的形成机制。
研究方法 本文对目前草莓状黄铁矿的形成机理、氧化还原环境的应用及后期环境变化的影响进行了系统的综合研究。
研究结果 不同氧化-还原环境下形成的草莓状黄铁矿在粒径、形态以及硫同位素之间均存在较大的差异，可做为反演古氧化-还原环境的指标。草莓状黄铁矿的微晶尽管与粒径具有一定的正相关性，但是两者在形态演化序列、生长模式、聚集因素等方面与古氧化-还原环境的关系尚不清楚。仅凭草莓状黄铁矿粒径与铬还原法测定的硫同位素反演古氧化-还原环境存在一定的局限性，需要其他指标综合判定，尚需进一步开展草莓状黄铁矿原位硫同位素值与粒径对古氧化-还原环境反演的研究。后期氧化可使草莓状黄铁矿表面化学成分发生变化，但粒径分布依然具有古氧化-还原环境的指示意义。
结论 草莓状黄铁矿的实验模拟、理论体系和多学科交叉的研究中仍存在一些问题，尚需进一步研究。
Abstract:This paper is the result of mineral exploration engineering.
Objective Framboidal pyrite are widespread in modern sediments and sedimentary rocks, widely considered organic or inorganic genesis. Although both formation mechanisms have theoretical and experimental support, a formation mechanism with general significance has not yet been established well.
Methods This paper systematically and comprehensively studies the formation mechanism of framboidal pyrite, the application of redox conditions, and the influence of later environmental changes.
Results The size and texture of pyrite framboids and the sulfur isotopes between framboids have fluctuated with the oxygen level. Therefore, framboidal pyrite is used as a reconstruct paleoenvironment proxy commonly. Although the microcrystallines of framboidal pyrite are correlated to the particle size positively, their (Morphological evolution sequence), growth patterns, (aggregation factors), as well as the relationship with paleo-redox are still poorly understood. The redox condition inverse from particle sizes of pyrite framboids and chromium reduction-determined sulfur isotope has certain limitations. Therefore, a comprehensive analysis of redox indicators is expected, which requiring further studies on links between in-situ sulfur isotope and particle sizes of framboidal pyrite. Although the framboidal surface chemistry can be modified as changes in late oxidation conditions, the size distribution of framboidal pyrite is still meaningful as a redox indicator.
Conclusions In brief, experimental simulations, theoretical systems, and interdisciplinary studies on framboidal pyrite are still challenging and require further research.
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图 1 扫描电镜下草莓状黄铁矿外形及微晶结构（据Ohfuji et al., 2005）
Figure 1.
图 2 “草莓状黄铁矿有机成因-中空间隔模式”（据MacLean et al., 2008修改）
Figure 2.
图 3 Wilkin和Barnes关于草莓状黄铁矿形成的模式图（据Wilkin et al., 1996；杨雪英等，2011）
Figure 3.
图 4 在25℃、0.1MPa的有限水体及沉积物环境下时间的对数与草莓状黄铁矿粒径关系图（据Rickard，2019）
Figure 4.
图 6 草莓状黄铁矿粒径在硫化环境和氧化-贫氧环境下的分布及明显的重叠分布（数据来源于Wilkin et al., 1996和Rickard, 2019）
Figure 6.
图 7 草莓状黄铁矿的平均粒径与标准偏差（a）、偏态系数（b）图解（据Wilkin et al., 1996；常华进等，2009）
Figure 7.
图 8 草莓状黄铁矿形态演化（据Merinero et al., 2008）
Figure 8.
图 9 黑海沉积物（a）和大盐沼沉积物（b）中草莓状黄铁矿粒径（D）与微晶直径（d）的关系（据Wilkin et al., 1996）
Figure 9.
图 10 四个地点微晶与草莓状粒径分布图（据Wilkin et al., 1996）
Figure 10.
图 11 室温下一种黄铁矿微晶形态的演化和生长示意图（据Wang and Morse, 1996）
Figure 11.
图 12 歧化反应过程中硫化物重复氧化为S0的模式图（据Canfield and Thamdrup, 1994）
Figure 12.
图 14 草莓状黄铁矿向自形黄铁矿演化的3种模式（据Sawlowicz，1993）
Figure 14.
图 15 草莓状黄铁矿的二次生长对结构的改变（据Wacey et al., 2015）
Figure 15.
表 1 根据溶解氧划分的古氧化-还原环境（据Tyson and Pearson, 1991）
Table 1. Classification of paleo-redox conditions based on dissolved oxygen (after Tyson and Pearson, 1991)
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表 2 草莓状黄铁矿粒径特征与古氧化-还原环境及沉积特征总结（据Bond and Wignall, 2010）
Table 2. Summary of characteristics used to define paleo-redox conditions during deposition(after Bond and Wignall, 2010)
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表 3 草莓状黄铁矿与草莓状黄铁矿氧化物粒径数据对比表（据黄元耕，2018）
Table 3. Comparison table of oxide particle size data of framboidal pyrite and framboidal pyrite (after Huang Yuangeng, 2018)
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