Mineral Ferric Iron Contents of Peridotite Xenoliths by Mössbauer Spectroscopy: Oxygen Fugacity Applications
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摘要: 利用地幔橄榄岩包体中平衡矿物对的氧逸度计可以有效限定岩石圈地幔的氧化-还原状态.本文使用中国地质大学（武汉）新购置的WSS-10型常温穆斯堡尔光谱仪对华北地块西北部狼山地区橄榄岩包体的四相矿物开展了铁价态的直接测定.结果显示，斜方辉石Fe3+/∑Fe为0.05~0.11，单斜辉石的为0.16~0.25，尖晶石的为0.16~0.22，橄榄石为0.利用橄榄石-斜方辉石-尖晶石氧逸度计，获得狼山地区岩石圈地幔氧逸度为FMQ-0.82至FMQ-0.39（均值为FMQ-0.65）.该值略高于依据电子探针测试数据计算获得的氧逸度值（FMQ-1.49至FMQ-0.8，均值为FMQ-1.25），造成这一差异的原因可能是后者忽略了尖晶石晶格中Fe3+过剩和阳离子空位导致的非化学计量比.与全球克拉通岩石圈地幔氧逸度值（均值为FMQ-0.35）相比，华北地块西北缘狼山地区岩石圈地幔整体表现为较还原状态，推测与深部地幔低fO2熔体上升交代有关.Abstract: The redox state of the lithospheric mantle can be estimated by well equilibrated mineral pairs of mantle peridotite xenoliths. Here we explore the mantle redox state of the northwest North China Craton by measuring the mineral Fe3+/∑Fe of the Langshan spinel lherzolite xenoliths using the newly established lab of WSS-10 Mössbauer spectroscopy at China University of Geosciences (Wuhan). The results show that the Fe3+/∑Fe ratios are 0.05-0.11 for orthopyroxene, 0.16-0.25 for clinopyroxene, 0.16-0.22 for spinel, and no Fe3+ was confirmed in olivine. The corresponding mantle oxygen fugacity using the olivine-orthopyroxene-spinel oxy-barometry is FMQ-0.82 to FMQ-0.39 (averaged at FMQ-0.65), slightly higher than the estimates using electron microprobe data (FMQ-1.49 to FMQ-0.8, averaged at FMQ-1.25). This discrepancy may be explained by the non-stoichiometry Fe3+ excess and cation vacancies in the spinel lattice, which is generally ignored in the stoichinometric calculation using electron microprobe data. Compared with global cratonic mantle (averaged at FMQ-0.35), the lithospheric mantle underneath the northwest North China Craton, represent by Langshan mantle xenoliths, is relatively reduced, and likely results from metasomatism by low-fO2 melts from deeper mantle domains.
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Key words:
- lithospheric mantle /
- oxygen fugacity /
- peridotite xenoliths /
- Mössbauer spectrometer /
- Fe3+/∑Fe /
- petrology
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图 1 狼山玄武岩中橄榄岩捕掳体野外(a)及橄榄岩包体显微镜下矿物组合照片(b)
矿物缩写：Ol.橄榄石；Opx.斜方辉石；Cpx.斜方辉石；Spl.尖晶石
Fig. 1. Field photo (a) and mineral assemblage microphotographs (b) of the peridotite xenoliths from the Langshan alkali basalts
图 2 穆斯堡尔光谱及相关参数(据Dyar et al., 2006)修改
a.同质异能位移（IS）和四极分裂（QS）；b.α-Fe磁超精细分裂（Hhf）；IS指穆谱中的单峰或双峰的中心位置与多普勒零速度之间的速度差；QS为双峰中两条吸收线中心的距离；磁超精细分裂（Hhf）指原子核处于核外电子形成的磁场中时，原子核能级进一步分裂后形成六线峰
Fig. 2. Mössbauer spectrum and Mössbauer parameters (after Dyar et al., 2006)
图 3 狼山地区地幔橄榄岩矿物的室温穆斯堡尔谱图
a.橄榄石（Ol）；b.单斜辉石（Cpx）；c.斜方辉石（Opx）；d.尖晶石（Spl）；橄榄石中Fe2+（Ⅰ）和Fe2+（Ⅱ）分别指配为Fe2+（M1）和Fe2+（M2）.单斜辉石和斜方辉石中Fe2+（Ⅰ）和Fe2+（Ⅱ）分别是Fe2+（M1）和Fe2+（M2），Fe3+在八面体M1位.尖晶石中Fe2+（Ⅰ）、Fe2+（Ⅱ）和Fe2+（Ⅲ）是四面体位置（A）上的不同Fe2+，Fe3+在八面体B位
Fig. 3. Mössbauer spectra of typical minerals of the Langshan peridotite xenoliths in room temperature
图 4 利用Mössbauer光谱和电子探针测定狼山橄榄岩捕虏体矿物中Fe3+/∑Fe比值比较(a)和依据Mössbauer光谱和电子探针测定Fe3+/∑Fe比值计算的ΔlgfO2(FMQ)值对比(b)
ΔFMQ（Wood91）指示氧逸度计来自Wood et al.（1990）结合Nell and Wood（1991）；ΔFMQ（Wood89+Frost91）指示氧逸度计来自Mattioli and Wood（1988）/Wood and Virgo（1989）结合Frost（1991）；ΔFMQ（Wood89+O’Neill87）指示氧逸度计来自Mattioli and Wood（1988）/Wood and Virgo（1989）结合O’Neill（1987）；ΔFMQ（Ball91）使用氧逸度计来自Ballhaus et al.（1991）
Fig. 4. Minerals Fe3+/ΣFe ratios calculated from EPMA analyses of Langshan peridotites plotted against Fe3+/ΣFe ratios of the same Minerals analyzed by Mössbauer spectroscopy (a). The comparison of ΔlgfO2(FMQ) was calculated based on Fe3+/∑Fe by EMPA and Mössbauer spectroscopy (b).
图 5 不同氧逸度计获取的ΔFMQMöss-EMPA差值与ΔFe3+/∑FeMöss-EMPA在狼山橄榄岩矿物尖晶石(a)和单斜辉石和斜方辉石(b)差值的比较
Fig. 5. Comparison of ΔFMQMöss-EMPA and Fe3+/∑Fe Möss-EMPA in spinel(a)、clinopyroxene and orthopyroxene(b) by different oxygen geobarometer.
图 6 狼山地区橄榄岩的氧逸度值与(a)全球典型构造地区产出橄榄岩氧逸度值对比和(b)华北克拉通地区产出橄榄岩依据探针数据计算氧逸度值比较；地幔橄榄岩的ΔlgfO2(FMQ)-Cr#(Sp)图解(c)
图例同图 4；数据来源：俯冲环境（Wood and Virgo, 1989；Brandon and Draper, 1996；Bénard et al., 2018）；深海环境（Bryndzia and Wood, 1990）；造山带橄榄岩地体（Woodland et al., 1992；Woodland et al., 2006）；大陆岩石圈地幔（Wood and Virgo, 1989；Canil et al., 1990；Ionov and Wood, 1992；Canil et al., 1994）；克拉通（McCammon and Kopylova, 2004；Goncharov et al., 2012）；华北克拉通（Zheng et al., 1998；Zheng et al., 2001；Zheng et al., 2005；Zheng et al., 2007；陈曦和郑建平，2009；余淳梅，2009；周媛婷等，2010）
Fig. 6. Comparison of the fO2 of the peridotites from the Langshan area with those for other typical tectonic regions mantle peridotites (a) and (b) mantle xenoliths from North China Craton and (c) ΔlgfO2(FMQ)-temperature diagrams of Langshan mantle peridotites.
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