Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS).We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ⁵⁶Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ⁵⁶Fe value (1‰) and a rim with a crustal δ⁵⁶Fe value (0‰). The observed isotopic zoning suggests that the positive δ⁵⁶Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis.The positive δ⁵⁶Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of ⁵⁶Fe-enriched ferric oxyhydroxide (Type 1) and ⁵⁶Fe depleted Fe²⁺aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ⁵⁶Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe²⁺aq steady-state model. The model calculation shows that half the Fe²⁺aq influx was oxidized in the seawater. This implies that O₂ produced by photosynthesis would have been completely consumed by oxidation of the Fe²⁺aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.     

Carbon isotope chemostratigraphy of a Precambrian/Cambrian boundary section in the Three Gorge area, South China: Prominent global-scale isotope excursions just before the Cambrian Explosion

Carbon isotope chemostratigraphy has been used for worldwide correlation of Precambrian/Cambrian (Pc/C) boundary sections, and has elucidated significant change of the carbon cycle during the rapid diversification of skeletal metazoa (i.e. the Cambrian Explosion). Nevertheless, the standard δ¹³C curve of the Early Cambrian has been poorly established mainly due to the lack of a continuous stratigraphic record. Here we report high-resolution δ¹³C chemostratigraphy of a drill core sample across the Pc/C boundary in the Three Gorge area, South China. This section extends from an uppermost Ediacaran dolostone (Dengying Fm.), through a lowermost Early Cambrian muddy limestone (Yanjiahe Fm.) to a middle Early Cambrian calcareous black shale (Shuijingtuo Fm.). As a result, we have identified two positive and two negative isotope excursions within this interval. Near the Pc/C boundary, the δ¹³C_carb increases moderately from 0 to + 2‰ (positive excursion 1: P1), and then drops dramatically down to − 7‰ (negative excursion 1: N1). Subsequently, the δ¹³C_carb increases continuously up to about + 5‰ at the upper part of the Nemakit–Daldynian stage. After this positive excursion, δ¹³C_carb sharply decreases down to about − 9‰ (N2) just below the basal Tommotian unconformity. These continuous patterns of the δ¹³C shift are irrespective of lithotype, suggesting a primary origin of the record. Moreover, the obtained δ¹³C profile, except for the sharp excursion N2, is comparable to records of other sections within and outside of the Yangtze Platform. Hence, we conclude that the general feature of our δ¹³C profile best represents the global change in seawater chemistry. The minimum δ¹³C of the N1 (− 7‰) is slightly lower than carbon input from the mantle, thus implying an enhanced flux of ¹³C-depleted carbon just across the Pc/C boundary. Hence, the ocean at that time probably became anoxic, which may have affected the survival of sessile or benthic Ediacaran biota. The subsequent δ¹³C rise up to + 5‰ (P2) indicates an increase of primary productivity or an enhanced rate of organic carbon burial, which should have resulted in lowering pCO₂ and following global cooling. This scenario accounts for the cause of the global-scale sea-level fall at the base of the Tommotian stage. The subsequent, very short-term, and exceptionally low δ¹³C (− 9‰) in N2 could have been associated with the release of methane from gas hydrates due to the sea-level fall. The inferred dramatic environmental changes (i.e., ocean anoxia, increasing productivity, global cooling and subsequent sea-level fall with methane release) appear to coincide with or occur just before the Cambrian Explosion. This may indicate synchronism between the environmental changes and rapid diversification of skeletal metazoa.     

Geochemistry of the oldest MORB and OIB in the Isua Supracrustal Belt, southern West Greenland: Implications for the composition and temperature of early Archean upper mantle

Abstract Recent geological investigations of the Isua Supracrustal Belt (3.8 Ga), southern West Greenland, have suggested that it is the oldest accretionary complex on earth, defined by an oceanic plate‐type stratigraphy and a duplex structure. Plate history from mid‐oceanic ridge through plume magmatism to subduction zone has been postulated from analysis of the reconstructed oceanic plate stratigraphy in the accretionary complex. Comparison between field occurrence of greenstones in modern and ancient accretionary complexes reveals that two types of tholeiitic basalt from different tectonic settings, mid‐oceanic ridge basalt (MORB) and oceanic island basalt (OIB), occur. This work presents major, trace and rare earth element (REE) compositions of greenstones derived from Isua MORB and OIB, and of extremely rare relict igneous clinopyroxene in Isua MORB. The Isua clinopyroxenes (Cpx) have compositional variations equivalent to those of Cpx in modern MORB; in particular, low TiO₂ and Na₂O contents. The Isua Cpx show slightly light (L)REE‐depleted REE patterns, and the calculated REE pattern of the host magma is in agreement with that of Isua MORB. Analyses of 49 least‐altered greenstones carefully selected from approximately 1200 samples indicate that Isua MORB are enriched in Al₂O₃, and depleted in TiO₂, FeO*, Y and Zr at the given MgO content, compared with Isua OIB. In addition, Isua MORB show an LREE‐depleted pattern, whereas Isua OIB forms a flat REE pattern. Such differences suggest that the Early Archean mantle had already become heterogeneous, depending on the tectonic environment. Isua MORB are enriched in FeO compared with modern MORB. Comparison of Isua MORB with recent melting experiments shows that the source mantle had 85–87 in Mg? and was enriched in FeO. Potential mantle temperature is estimated to be approximately 1480°C, indicating that the Early Archean mantle was hotter by at most approximately 150°C than the modern mantle.     

Internal structures and U–Pb ages of zircons from a tuff layer in the Meishucunian formation, Yunnan Province, South China

The Precambrian/Cambrian (PC/C) boundary is one of the most important intervals for the evolution of life, represented by prominent biological evolution from the first appearance of soft-bodied animals from the late Neoproterozoic to the sudden diversification of animals with mineralized skeletons in the Cambrian. In South China several areas contain many fossils and are well exposed, suitable for the investigation of PC/C boundary. However, geochronological relationships are still poorly known because of lack of combined detailed investigations of internal structures of zircons and in-situ U–Pb dating.We focus on the internal structure of zircons from a tuff layer within Bed 5 in the Meishucun section on which we undertook cathodoluminescence (CL) imaging and in-situ U–Pb dating with LA-ICP-MS and nano-SIMS. Over 600 zircons from the tuff layer were classified into three types based on their CL images: oscillatory rims, inherited cores and dull structures. U–Pb dating of the internal structure of the zircons by LA-ICP-MS clearly shows a distinct unimodal age population dependent on the structure: 531 ± 17 Ma for the oscillatory rims and 515 Ma for the dull structures. The clear oscillatory zonation, the prismatic morphology, and their occurrence indicate that the oscillatory rims were formed from felsic magmatism, and that the U–Pb nano-SIMS age of 536.5 ± 2.5 Ma records the depositional age of the tuff. Our results indicate that the PC/C boundary is situated below Bed 5, and therefore the bottom of Zone 1 (Marker A) is more appropriate for the PC/C boundary than is the top of Zone 1 (Marker B). The age of a positive anomaly (P2) in the early Cambrian is estimated to be ca. 536 Ma.     

Indicator of paleosalinity: Sedimentary sulfur and organic carbon in the Jurassic–Cretaceous Tetori Group,central Japan

A simple geochemical technique using the ratio of total sulfur (TS) to total organic carbon (TOC) was successfully used to reconstruct paleoenvironments in the Jurassic–Cretaceous Tetori Group, central Japan. The TS to TOC ratio is often employed as an effective parameter to separate modern marine or brackish sediments from freshwater deposits. To test the TS/TOC method for paleoenvironmental interpretation of the Tetori Group, we first analyzed TS/TOC for samples for which depositional conditions (i.e. marine, brackish or freshwater) had been recognized paleontologically. The results indicate that the method can effectively separate sedimentary rocks deposited under freshwater from marine and brackish settings. Once we had established the effectiveness of this method, we applied it to three sections of the Tetori Group, central Japan. Stratigraphic fluctuations in TS/TOC values revealed episodic incursions of marine or brackish conditions in the dominantly freshwater depositional sequence in the middle of the Jobu Formation of the Itoshiro Subgroup at the Izumi section, Fukui Prefecture. The same paleoenvironment is also suggested to occur at the top of the Tetori Group in the Tateyama section, Toyama Prefecture. This research provides important information to paleogeographers who currently lack evidence from facies fossils to indicate if the uppermost part of the Tetori Group represents marine or brackish settings. A chemostratigraphy of TS/TOC parameters potentially could provide a correlation among Jurassic–Cretaceous sequences along continental margins over East Asia.     

Rare earth element distribution in the Melrose-b howardite: Pre-terrestrial negative Ce anomaly

In order to investigate the genetic nature of the polymict breccia howardite Melrose-b, a whole-rock sample was separated into four fractions after pulverization and the rare earth element (REE) abundances were precisely determined by isotopic dilution in those fractions. Such an investigation shows that the three precipitated fine-particle fractions are depleted in Ce by the same factor (0.62 ～ 0.64) in spite of differences in mineralogy, while the corresponding factor of Ce depletion for the suspended-matter fraction is 0.462; the smaller value indicates a greater depletion in Ce.The weight fraction values of four fractions calculated from the REE abundances are in satisfactory agreement with the actual values. The concentration ratios between plagioclase and mainly pigeonite fractions accord with those observed in similar phases of the Juvinas eucrite [1]. Moreover, the bulk pattern synthesized from the three fine-particle fractions is similar in absolute level to that for the Zmenj howardite [1]. It is concluded that the negative Ce anomaly reflects the effect predating the igneous activity in the parent planetary body.     

Chemical composition of HAL,an isotopically-unusual Allende inclusion

Thirty-seven major, minor and trace elements were determined by INAA and RNAA in samples of hibonite, black rim and portions of friable rim from an unusual Allende inclusion, HAL. The peculiar isotopic, mineralogical and textural properties of HAL are accompanied by very unusual trace element abundances. The most striking feature of the chemistry is the virtual absence of Ce from an inclusion otherwise highly enriched in REE compared to Cl chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os and Ir, relative to other refractory elements. Of the lithophile elements determined which are normally considered to be refractory in a gas of solar composition, Sr, Ba, Ce, U and V are the most volatile in oxidizing gases. The distribution of REE between hibonite and rims seems to have been established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. On the basis of HAL's chemical and isotopic composition, possible locations for the chemical and mass dependent isotopic fractionation are in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.     

Damping identification of a full‐scale passively controlled five‐story steel building structure

A series of large‐scale dynamic tests was conducted on a passively controlled five‐story steel building on the E‐Defense shaking table facility in Japan to accumulate knowledge of realistic seismic behavior of passively controlled structures. The specimen was tested by repeatedly inserting and replacing each of four damper types, that is, the buckling restrained braces, viscous dampers, oil dampers, and viscoelastic dampers. Finally, the bare steel moment frame was tested after removing all dampers. A variety of excitations was applied to the specimen, including white noise, various levels of seismic motion, and shaker excitation. System identification was implemented to extract dynamic properties of the specimen from the recorded floor acceleration data. Damping characteristics of the specimen were identified. In addition, simplified estimations of the supplemental damping ratios provided by added dampers were presented to provide insight into understanding the damping characteristics of the specimen. It is shown that damping ratios for the specimen equipped with velocity‐dependent dampers decreased obviously with the increasing order of modes, exhibiting frequency dependency. Damping ratios for the specimen equipped with oil and viscoelastic dampers remained constant regardless of vibration amplitudes, whereas those for the specimen equipped with viscous dampers increased obviously with an increase in vibration amplitudes because of the viscosity nonlinearity of the dampers. In very small‐amplitude vibrations, viscous and oil dampers provided much lower supplemental damping than the standard, whereas viscoelastic dampers could be very efficient. Copyright © 2012 John Wiley & Sons, Ltd.     

1679年三河-平谷8级地震破裂带的大地切片实验研究

大地切片调查法,就是在不搅动的状态下从地下切出未固结的第四纪浅部地层的垂直断片,它是一种较新的活动断层探测技术。发生在1679年9月2日的三河-平谷8级地震(烈度Ⅺ),是北京及附近地区历史上记录到的最大地震。在该地震的宏观震中——潘各庄附近,运用大地切片调查法对该地震破裂带进行了实验性探测,获得了较好的效果。实验研究表明:大地切片保留了完好的沉积细结构特征;大地切片调查实施时,要选择合适的动力源,对于北京平原这种黏土含量较高的沉积层,挖掘机加振动锤的动力组合优于吊车加振动锤的动力组合;大地切片由于振动会造成一定地层厚度的压缩,但黏土含量较高的北京地区,压缩比例基本<5%。另外,结合探槽和大地切片的对比分析,揭示了最近2次古地震事件,分别是1679年事件和该地震之前的一次事件,两次地震的垂直同震位移分别是1·4m和1·2m