地球历史中的巨型氧化作用事件:了解古地理背景演变的重要线索*

在塑造我们的星球环境的过程之中,分子氧起着关键的作用。大气圈和海洋中氧气的出现及其浓度随着时间的变化,与地球上的主要变化存在强烈关联,诸如构造重组、气候波动和生物进化。针对地球大气圈氧气含量的上升,多年研究的结果肯定了2个基本事实:(1)地球最早期的大气圈是缺乏氧气的;(2)今天的大气圈则为21%的氧气所组成。由于地质历史时期大气圈氧气水平的大多数地质标志,只是意味着存在与缺乏,这就为确定大气圈氧气含量上升的时间进程带来很多困难。即使如此,一系列地质证据已经表明,一个从缺氧的到含氧的大气圈的转变,大致发生在2.5—2.0,Ga,这个转变被定义为巨型氧化作用事件(GOE)。近年来的深入研究发现,几个主要证据表明,在前寒武纪—寒武纪过渡时期的大约850—540,Ma,发生了“第二次巨型氧化作用事件(GOE-Ⅱ)”,还被进一步定义为新元古代巨型氧化作用事件(NOE)。再者,大气圈氧气水平在显生宙还存在着一个特别的上升,这次变化在石炭纪晚期接近一个峰值为150% PAL(现代大气圈氧气含量水平),所以,也可以定义为一次巨型氧化作用事件,即显生宙的巨型氧化作用事件(POE)。因为蓝细菌光合作用造成的氧气生产,曾经导致了大气圈与海洋的氧化作用,反过来为需氧呼吸作用和大型而且复杂的、最终富有智慧的生物进化,提供了基本条件;因此,大气圈氧气上升,是与地球动力学过程紧密相关的地球生物学过程的作用结果,从而成为了解漫长的地质历史时期古地理背景演变的重要线索。从古元古代的GOE,经过新元古代的NOE,到显生宙的POE,这些巨型氧化作用事件的内在特征、作用结果与基本属性,尽管存在着较大的差异,但是,从这些概念的出现到对它们的形成机理的探索性研究,涌现出了许多新概念和新认识;追索这些新概念和新认识,将为了解地球大气圈氧气上升的复杂历史所代表的一个特别的地球上生物学过程,提供一些有益的重要线索和思考途径。     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.     

Fluctuations in late Neoproterozoic atmospheric oxidation — Cr isotope chemostratigraphy and iron speciation of the late Ediacaran lower Arroyo del Soldado Group (Uruguay)

Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (δ⁵³Cr up to + 5.0‰) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (Fe_HR) to total iron (Fe_tot) which indicate a predominance of anoxic water columns (Fe_HR/Fe_tot > 0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd T_DM model ages = 2.1–2.2 Ga) provenance typical of the Rio de la Plata Craton. The association of positive δ⁵³Cr–ferruginous (Fe_HR/Fe_tot > 0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian–Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian–Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic.     

金属稳定同位素示踪地球增氧事件

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.      

Ocean Redox State at 2500‒500 Ma: Modern Concepts

Modern concepts on variations of the redox conditions of Proterozoic ocean and atmosphere are reviewed. Generalized data indicate a non-linear evolution of the О₂ content in atmosphere and ocean for almost 2 Ga of the geological history. Contrasting distribution of minimum and maximum values of diverse proxies of the ocean redox state was found for the Great Oxygenation Event, Early–Late Proterozoic transition stage, and the Late Precambrian–beginning of Cambrian. The last interval is marked by a wide scatter of Mo, V, and U_sed concentrations and values of Мо/TOC, δ⁹⁸Mo, δ⁵³Cr, and δ⁸²Se in different geological objects. This time interval also coincided with one more large-scale oxygenation event, Neoproterozoic. Thus, according to the modern concepts, the О₂ contents near the Earth’s surface and in ocean significantly varied during the entire Proterozoic. These concepts are consistent with the assumption by Frolov and many other researchers concerning the heterogeneous distribution of рН and Eh in ancient hydrosphere and the existence of diverse, sufficiently contrasting “gas” facies. They also agree with conclusions by Sochava that the periodical variations of О₂ content in atmosphere and hydrosphere, especially at the Precambrian–Phanerozoic boundary, are related to the mass extinctions, emergence of adaptive response of animals (appearance of exoskeletons, food search strategy change, and others) and heavy taxonomic radiation of the latters.     

大火成岩省与大规模黑色页岩沉积的成因联系及其意义

大火成岩省对全球性大气-海洋环境的巨变及生物灭绝有非常重要的影响。已有研究结果表明,显生宙（即寒武纪以来）大火成岩省与全球大洋缺氧与生物灭绝有明显的成因联系,显生宙国际地质年代表中多个金钉子均与以大火成岩省、黑色页岩及生物灭绝为代表的全球性地质事件相对应。但由于对前寒武纪,特别是"地球中年期"（18~8亿年,"枯燥的10亿年"）大气氧浓度、海洋的氧化-还原状态及生物门类及演化认识的局限性,关于前寒武纪大火成岩省与环境的影响及其与黑色页岩沉积的成因联系一直很不清楚。通过对全球哥伦比亚（奴那）超大陆中约13.8亿年全球性大火成岩省及黑色页岩沉积时空分布的研究,发现这些大火成岩省及黑色页岩的分布有明显的规律。约13.8亿年大火成岩省广泛分布在北美、格陵兰、西伯利亚、波罗地、卡拉哈里、刚果、西非、亚马逊、南极及西澳大利亚等大陆上;而同期的黑色页岩在华北及北澳大利亚克拉通广泛分布,在西伯利亚、巴西及印度等克拉通也有分布。根据这些黑色页岩在超大陆重建图中的空间分布,提出了哥伦比亚（奴那）超大陆中这些广泛分布的约13.8亿年黑色页岩可能沉积于连通的大型海相盆地,而不是以往所认为的局部封闭的小盆地。通过约13.8亿年大火成岩省与黑色页岩内火山灰（斑脱岩）年龄的对比,进一步提出约13.8亿年存在一次与全球性大火成岩省有关的大洋缺氧事件,以此期大火成岩省与黑色页岩为代表的全球性地质事件为中元古代盖层系与延展系提供了精确的界限年龄为1383 Ma。初步的研究结果还显示,"地球中年期"可能还有多期的大火成岩省与黑色页岩沉积有时空联系,有望为晚前寒武纪地质年代表划分提供新的事件约束。      

生命起源、早期演化阶段与海洋环境演变

近年的研究表明,地球生命可能起源于距今39~36亿年之间。除了碳元素以外,水、氮、氢、磷等元素也是生命起源的必备条件,黏土矿物和金属硫化物是有机质合成的重要催化剂,有热液活动的碱性热水环境是最有利生命发生的孵化场。自原核生物在约3.5 Ga出现之后,生命就一直表现为与环境的协同进化关系。大气圈氧化是地球史上最重大的地质事件之一,它不仅改变了地球表层环境条件、加速了表生地质过程和新矿物的产生,而且改变了海洋化学条件和元素循环。大气圈氧化事件的根本在于产氧蓝细菌的出现,元古宙中期海洋化学性质的整体转换也与微生物过程密切相关。新元古代多细胞生物的繁盛和末期后生动物的出现及其在寒武纪初期的快速多样化是生物圈演化的重大飞跃。这个过程也与海洋氧化增强及其导致的海洋化学变化密切相关,其中硫化水域消失和减弱以及海水中微营养元素可得性增加可能是重要因素,这也与微生物过程直接相关。     

Tellurium,selenium and cobalt enrichment in Neoproterozoic black shales,Gwna Group,UK: Deep marine trace element enrichment during the Second Great Oxygenation Event

Black shales of the late Neoproterozoic Gwna Group (570–580 Ma), UK, contain enrichments of tellurium (Te), selenium (Se) and cobalt (Co) relative to average shale compositions. The Te and Co enrichments bear comparison with those of ferromanganese crusts in the modern deep ocean. Gwna Group deposition coincides with the Second Great Oxidation Event, which had a significant effect on trace element fixation globally. Selenium and Te concentrations within these black shales indicate increased continental weathering rates, high biological productivity and corresponding increases in atmospheric O₂ concentrations. Cobalt, nickel (Ni) and arsenic (As) enrichments in this succession are secondary mineralisation phases. Demand for many of the trace elements found enriched in the Gwna Group black shales make their mechanisms of accumulation, and variations through the geological record, important to understand, and suggests that new resources may be sought based on black shale protoliths from this period.     

Ediacaran seawater temperature: Evidence from inclusions of Sinian halite

Seawater temperatures throughout Earth's history have been suggested to illustrate a long-term cooling trend from nearly 70 °C at ～3500 Ma to around 20 °C at ～800 Ma. The terminal Neoproterozoic prior to the “Cambrian Explosion” is a key interval in evolutionary history, as complex multicellularity appeared with the advent of the Ediacara fauna. These organisms were likely the first that required higher levels of atmospheric and dissolved marine oxygen for their sustainability. It is known that most modern macroinvertebrates are intolerant of temperatures in excess of 45 °C. Perhaps more importantly, these high seawater temperatures limit the potential of dissolved oxygen, and therefore become an integral part of this evolutionary story. Previously, our understanding of seawater temperature during the terminal Neoproterozoic comes only from ¹⁸O/¹⁶O and ³⁰Si/²⁸Si ratios ascertained from a limited number of cherts. Isotopic ratio methods for assessing seawater temperatures are inherently indirect and have a wide range of oscillation. However, maximum homogenization temperatures (Th_max) of primary fluid inclusions in halite provide a direct means of assessing brine temperature, and have been shown to correlate well with average maximum air temperatures. The oldest halites date to the Neoproterozoic–lower Paleozoic (～700–500 Ma), and Ediacaran representatives can be found in Sichuan Province, China, which do preserve primary fluid inclusions for analysis via cooling nucleation methods. We utilized halite samples from the Changning-2 well, correlative to the Dengying Formation (551–542 Ma), to provide a direct assessment of terminal Neoproterozoic seawater temperature. Our measurements indicate that seawater temperatures where these halites formed are highly similar to tropical Phanerozoic seawater temperature estimates. From compiled paleotemperature data, the decline in seawater temperatures over the course of the Proterozoic, accompanied by the reduction of seawater salinity with the sequestration of salt in massive halite deposits in the Neoproterozoic, allowed the ocean system to accumulate more dissolved oxygen, and potentially paved the way for the evolutionary innovation of complex multicellularity.     

Duration and synchroneity of the largest negative carbon isotope excursion on Earth: The Shuram/Wonoka anomaly

Carbonate δ¹³C values provide a useful monitor of changes in the global carbon cycle because they can record the burial ratio of organic to carbonate carbon. The most pronounced isotope excursions in the geologic record occur during the Neoproterozoic and have assumed a central role in the interpretation of biogeochemical events preceding the Ediacaran and Cambrian radiations. The most profound negative carbon isotope excursion is best recorded in the Ediacaran-aged Shuram Formation of Oman and has potential equivalents worldwide including the Wonoka Formation of South Australia and other sections in China, India, Siberia, Canada, Scandinavia and Brazil. All these excursions are less well understood than those in the Phanerozoic because of their unusual magnitude, long duration (> 1 Ma) and the difficulty in correlating Neoproterozoic basins to confirm independently that they do indeed record global change in the mixed ocean reservoir. Alternatively, these δ¹³C anomalies could reflect diachronous diagenetic processes. Currently none of these excursion are firmly time constrained and critical to their interpretation is a coherent reproducibility and synchroneity at the global ocean scale. Here we use available strontium isotope record as an independent chronometer to test the timing and synchroneity of the Shuram δ¹³C and its potential equivalents. The use of the ⁸⁶Sr/⁸⁷Sr ratio allows the reconstruction of a coherent, global δ¹³C record calibrated independently against time. The calibrated δ¹³C curve indicates that the Shuram negative anomaly spans several tens of millions of years and reaches values below −10‰. This carbon isotopic anomaly therefore represents a meaningful oceanographic event that fundamentally challenges our understanding of the carbon cycle as defined in the Phanerozoic.     

Re-Os同位素在晚新元古代至早寒武世测年及古环境演绎中的应用进展

晚新元古代至早寒武世是地球演化历史上极其重要的时期,该时期地层年龄框架的厘定以及古海水、古大气、古气候等方面的研究一直是国际地学界的关注热点。Re-Os同位素测年法是近十几年来兴起的地层测年法,其对于晚新元古代至早寒武世重要时间节点上沉积的富有机质黑色页岩具有测年及示踪古环境的双重优势。本文以晚新元古代至早寒武世地层为例,阐述了Re-Os同位素测年法在年代地层学研究中的应用,通过与大量的、精确的锆石U-Pb年龄对比,论证了Re-Os同位素测定沉积地层年龄的可靠性。对于震旦系陡山沱组地层建阶及留茶坡组地层的年代学研究,黑色页岩Re-Os同位素测年法可发挥重要的作用。结合前人所做的Sr同位素变化曲线以及收集的晚新元古代—早寒武世Os同位素初始值的测试数据,阐述了Os同位素在该时段古环境演绎及Ni-Mo-V多金属层来源追溯上发挥的作用。黑色页岩难以进行~(87)Sr/~(86)Sr的分析,而Os同位素初始值能较好地弥补这一缺陷,二者的相互结合将为晚新元古代至早寒武世古环境演化的研究作出贡献。本文指出,随着Re-Os同位素分析技术的发展以及更多实验流程的建立,该项技术在未来年代地层学,尤其对一些古老地层的年代厘定具有广阔的应用前景。     

大气圈氧气含量水平上升的时间进程:一个与地球动力学过程紧密相关的地球生物学过程

两种气体,氮气和氧气,以压倒优势的状态主导着地球的大气圈。氮气是原生的,而且其存在和丰度不是生物过程所驱动的;相反,氧气是生物通过水的氧化作用而连续产生的,这个氧化作用得到了太阳光的能量驱动。氧气,一种对动物生命进化最为关键的气体,是如何变成大气圈中丰度第2的气体?问题并非以前所设想的那么简单;为了了解大气圈氧化的时间进程,我们不但要知道氧气是什么时候而且是如何第1次出现的,而且还要知道氧气是如何在大气圈中保持一个高浓度的。可以肯定的2个事实是:地球最早期的大气圈是缺乏氧气的,而今天的大气圈则为21%的氧气所组成。需要特别强调的是,大多数古代大气圈氧气水平的地质标志,只是意味着存在与缺乏,而且发生在以下2个时间点的大多数事件是高度不肯定的;但是,一系列地质证据已经表明,大气圈氧气含量水平上升的时间进程发生在2个时间点上:(1)一个从缺氧的到含氧的大气圈的转变,大致发生在2.0~2.5,Ga期间,这个转变就是著名的巨型氧化作用事件(GOE);(2)发生在前寒武纪-寒武纪过渡时期的大约540~850,Ma的第2次巨型氧化作用事件(GOE-Ⅱ),被进一步命名为新元古代氧化作用事件(NOE)。GOE与NOE,就得出了地球大气圈氧气含量水平上升三段式的盛行图像。随着研究的深入,得到了以下重要认识:如果说大气圈氧气含量的总体增加,从太古宙微不足道的水平增加到今天21%,是由于氧气生产作用增强的结果而代表了一个复杂的地球生物学过程的话,那么,这个过程则发生在随着侵蚀作用与沉积作用相对于火山活动而变得更加重要的状况下,更进一步讲,叠加在这个总体趋势下的则是一系列的阶梯式的氧气含量水平上升,这与超大陆聚合作用之后异常高的沉积作用周期是相联系的,从而进一步说明了大气圈氧气含量水平上升是与地球动力学过程紧密相关的地球生物学过程的作用结果。大气圈氧气含量水平一系列的阶梯式的上升,被总结为7个事件而与超大陆汇聚事件得到了良好的对比,从而提供了一个更加清晰的图像;也就是说,在超大陆汇聚作用之后,得到增强的沉积作用促进了大部分有机碳和黄铁矿的埋藏,因而阻碍了它们与自由氧的反应,结果就是大气圈氧气含量水平的实质性上升。新颖的观点和重要的认识,为深入理解地球大气圈氧气含量水平上升这一个重要的地球生物学过程,提供了重要的思考途径和研究线索;追索这些研究进展,将有助于揭开地球大气圈演变历史的神秘面纱并寻找出更多的科学研究生长点。     

黑色页岩的 Re－Os 同位素定年

Re－Os 同位素是近年来发展起来的一种新的同位素技术，既可用于定年又能用于示踪。国际上如何对沉积岩进行精确定年一直是个难题。近年来的研究表示，Re－Os 同位素可以用于黑色页岩的精确定年，同时可用于示踪古海洋环境。笔者对华南下寒武统牛蹄塘组黑色页岩开展了 Re－Os 同位素定年研究，获得的等时线年龄为537±10Ma。     

Detrital zircon geochronology of quartzites from the southern Madurai Block,India: Implications for Gondwana reconstruction

Detrital zircons are important proxies for crustal provenance and have been widely used in tracing source characteristics and continental reconstructions. Southern Peninsular India constituted the central segment of the late Neoproterozoic supercontinent Gondwana and is composed of crustal blocks ranging in age from Mesoarchean to late Neoproterozoic–Cambrian. Here we investigate detrital zircon grains from a suite of quartzites accreted along the southern part of the Madurai Block. Our LA-ICPMS U-Pb dating reveals multiple populations of magmatic zircons, among which the oldest group ranges in age from Mesoarchean to Paleoproterozoic (ca. 2980–1670 Ma, with peaks at 2900–2800 Ma, 2700–2600 Ma, 2500–2300 Ma, 2100–2000 Ma). Zircons in two samples show magmatic zircons with dominantly Neoproterozoic (950–550 Ma) ages. The metamorphic zircons from the quartzites define ages in the range of 580–500 Ma, correlating with the timing of metamorphism reported from the adjacent Trivandrum Block as well as from other adjacent crustal fragments within the Gondwana assembly. The zircon trace element data are mostly characterized by LREE depletion and HREE enrichment, positive Ce, Sm anomalies and negative Eu, Pr, Nd anomalies. The Mesoarchean to Neoproterozoic age range and the contrasting petrogenetic features as indicated from zircon chemistry suggest that the detritus were sourced from multiple provenances involving a range of lithologies of varying ages. Since the exposed basement of the southern Madurai Block is largely composed of Neoproterozoic orthogneisses, the data presented in our study indicate derivation of the detritus from distal source regions implying an open ocean environment. Samples carrying exclusive Neoproterozoic detrital zircon population in the absence of older zircons suggest proximal sources in the southern Madurai Block. Our results suggest that a branch of the Mozambique ocean might have separated the southern Madurai Block to the north and the Nagercoil Block to the south, with the metasediments of the khondalite belt in Trivandrum Block marking the zone of ocean closure, part of which were accreted onto the southern Madurai Block during the collisional amalgamation of the Gondwana supercontinent in latest Neoproterozoic–Cambrian.     

黔东震旦-寒武系转换期碎屑锆石年龄及其地质意义

通过对注溪地层剖面岩性、含矿性及接触关系进行详细考察,及对其黑色岩系中长石岩屑砂岩进行碎屑锆石LA-ICP-MS U-Pb测年,获得84组有效年龄,其中864~742 Ma年龄最集中,表明新元古代黔东地区存在大规模的岩浆活动.江南造山带为黔东早寒武世黑色岩系的主要沉积物源区,而钒等成矿元素源于基性-超基性侵入岩体.雪峰运动导致这些含矿岩体剥顶,大量金属元素注入海洋.海侵海底缺氧,富含这些成矿元素藻类死亡,钒等金属元素随同有机质进入沉积物中,在利于其沉淀富集的留茶坡和九门冲组地层成矿.536 Ma为留茶坡组最后接受沉积时限和九门冲组最大沉积年龄,震旦与寒武系界线位于留茶坡组中上部硅质岩中,清水江组地层岩性的变形、变质和角度不整合于上覆、下伏地层的现象为雪峰运动地质效应.      

A paired sulfate-pyrite δS approach to understanding the evolution of the Ediacaran-Cambrian sulfur cycle

An anomalous enrichment in marine sulfate δ³⁴S_SO4 is preserved in globally-distributed latest Ediacaran-early Cambrian strata. The proximity of this anomaly to the Ediacaran-Cambrian boundary and the associated evolutionary radiation has invited speculation that the two are causally related. Here we present a high-resolution record of paired sulfate (δ³⁴S_SO4) and pyrite (δ³⁴S_pyr) from sediments spanning ca. 547-540 million years ago (Ma) from the Ara Group of the Huqf Supergroup, Sultanate of Oman. We observe an increase in δ³⁴S_SO4 from ∼20‰ to ∼42‰, beginning at ca. 550 Ma and continuing at least through ca. 540 Ma. There is a concomitant increase in δ³⁴S_pyr over this interval from ∼ −15‰ to 10‰. This globally correlative enrichment, here termed the Ara anomaly, constitutes a major perturbation to the sulfur cycle. The absolute values of δ³⁴S_pyr reported here and in equivalent sections around the world, require the isotopic composition of material entering the ocean (δ³⁴S_in) to be significantly more enriched than modern (∼3‰) values, likely in excess of 12‰ during the late Ediacaran-early Cambrian. Against this background of elevated δ³⁴S_in, the Ara anomaly is explained not by increased fractionation between sulfate and pyrite (Δδ³⁴S), but by an increase in pyrite burial (f_pyr), most likely driven by enhanced primary production and sequestration of organic carbon, consistent with earlier reports of elevated organic carbon burial and widespread phosphorite deposition.     

Phosphogenesis of phosphorite from the Sinian Doushantuo Formation in Guizhou Province and its coupling relation with the Neoproterozoic Oxygenation Event

Phosphate deposits of the Ediacaran Doushantuo Formation accumulated in the central Guizhou Province are the typical phosphate-rich sediments during the Neoproterozoic Phosphogenic Episodes,which occurred after the “Snowball Earth”period and Neoproterozoic Oxygenation Event. However,the mechanisms of phosphate enrichment in seawater have always been hotly debated,and the research for correlations between phosphogenesis and transition of Ediacaran palaeo-ocean environments is still unsubstantial. This study focused on the sedimentological,petrological,mineralogical and geochemical analyses on the Doushantuo pristine phosphorite in Weng'an,Zunyi and Danzhai area. Documented by spherulitic phosphorites in the Lower Phosphorite beds from Weng'an area that contain abundant autogenetic Fe-bearing minerals such as pyrite and glauconite and show weak Ce negative anomaly,Fe-redox pumping in low-oxygen environments are the important phosphogenesis mechanism but only limited in coastal waters in the Early Doushantuo Period. Phosphorite in the Upper Phosphorite beds deposited within organic-rich beds and contain massive biological fossils suggests that phosphogenesis might have been triggered by degradation of organic matter and biological action in the Late Doushantuo Period,and distribution of phosphatic sediments extended to the deeper shelf to slope setting. Obvious Ce negative anomaly implies the increase of oxygen content in seawater. The transition of phosphogenesis mechanisms and the expansion of phosphorite deposits are the sedimentary response of ocean oxygenation,and the associated evolution of metazoans also changed the redox conditions of the deep seawater. These sedimentary and geochemistry data reflect the closed coupling relation between Doushantuo phosphorite in Guizhou Province and the Neoproterozoic Oxygenation Event.     

贵州震旦系陡山沱组磷块岩成磷作用及与新元古代末期氧化事件(NOE)的耦合*

新元古代末期历经“雪球地球”和大气、海洋增氧事件后,发生了全球性成磷事件,贵州省震旦系陡山沱组大规模磷矿床沉积是本次成磷事件的典型代表。然而现阶段对贵州陡山沱组磷块岩成磷作用机制研究存在诸多争议,成磷事件与同期古海洋环境转变之间的关联研究也较为薄弱。作者以贵州省瓮安、遵义和丹寨地区陡山沱组原生磷块岩为研究对象开展的沉积学、岩石学、矿物学和地球化学特征研究表明: 陡山沱早期成磷作用被限制在浅水海岸,瓮安地区A矿层球粒磷块岩中大量的含铁自生矿物黄铁矿、海绿石以及无Ce负异常指示的贫氧沉积水体环境均表明,Fe-氧化还原泵成磷模式在富磷过程中发挥了重要作用;陡山沱晚期磷块岩分布扩散至较深水陆棚—斜坡沉积相区,磷块岩与富有机质岩层共生,矿物晶体形态特征与矿石内富含的大量生物化石均表明,有机质沉降聚磷作用和生物成磷作用促使磷块岩大量沉积,较明显的Ce负异常值也指示了海水氧气含量的提升。成磷作用模式的转变和磷块岩分布的扩展是对海洋增氧事件的沉积响应,同时造成的多细胞动物演化也影响了深部水体的氧化还原状态,进而反映了贵州省陡山沱组磷块岩大规模沉积与新元古代末期氧化事件(NOE)密切的耦合关系。     

The Pacific Gondwana margin in the late Neoproterozoic–early Paleozoic: Detrital zircon U–Pb ages from metasediments in northwest Argentina reveal their maximum age,provenance and tectonic setting

U–Pb detrital zircon ages are reported from Puncoviscana Formation (late Neoproterozoic–Early Cambrian) and Mesón Group (Late Cambrian) greywackes of northwest Argentina, to constrain provenance and depositional environment.The new data are combined with previously-published detrital zircon ages, to show that Puncoviscana Formation age patterns contain two broad groups: late Mesoproterozoic–early Neoproterozoic (1150–850 Ma) and late Neoproterozoic–Early Cambrian (650–520 Ma); with their relative proportions varying inversely with youngest component age. The 1150–850 Ma age components are dominant in greywackes with oldest late Neoproterozoic components > 600 Ma. The former diminish considerably when late Neoproteozoic components become dominant and younger, to 520 Ma. A northernmost greywacke sample from Purmamarca, Jujuy, is distinctive: whilst its zircon age pattern partly resembles other Puncoviscana Formation samples, it contains no Cambrian–late Neoproterozoic ages, the youngest ages being early Neoproterozoic. This may reflect an early, Neoproterozoic, passive-margin depocentre for the Formation, or an older (early Neoproterozoic) succession within it, which may predate the Brasiliano orogeny in Brazil. The youngest age components, c. 520 Ma, in a greywacke from Rancagua (Cachi, Salta province), dominate an almost unimodal pattern suggestive of contemporary volcanic sources at a late Early Cambrian depocentre. Detrital zircon age patterns of the Mesón Group (Lizoite Formation) have major Cambrian–latest Neoproterozoic components resembling those of the Puncoviscana Formation, but its Mesoproterozoic component is diminished, and there are no significant age components of this age. Small youngest components at c. 500 Ma suggest a maximum Late Cambrian stratigraphic age. The Puncoviscana Formation detrital zircon patterns suggest a provenance in a continental hinterland having a stabilised, extensive late Mesoproterozoic orogen (with minor Paleoproterozoic and Archean precursors), and a more variable late Neoproterozoic orogen containing an evolving sequence of less extensive subcomponents. A direct relationship with the Brazilian Shield is suggested; with sediment supplies originating within active-margin orogens of the interior and collisional orogens at the suture between African and South American cratons, but ultimate deposition in passive-margin environments of western Gondwanaland.     

Neoarchean atmospheric chemistry and the preservation of S-MIF in sediments from the São Francisco Craton

Sulfur mass-independent fractionation (S-MIF) preserved in Archean sedimentary pyrite is interpreted to reflect atmospheric chemistry. Small ranges in Δ³³S that expanded into larger fractionations leading up to the Great Oxygenation Event (GOE; 2.45–2.2 Ga) are disproportionately represented by sequences from the Kaapvaal and Pilbara Cratons. These patterns of S-MIF attenuation and enhancement may differ from the timing and magnitude of minor sulfur isotope fractionations reported from other cratons, thus obscuring local for global sulfur cycling dynamics. By expanding the Δ³³S record to include the relatively underrepresented São Francisco Craton in Brazil, we suggest that marine biogeochemistry affected S-MIF preservation prior to the GOE. In an early Neoarchean sequence (2763–2730 Ma) from the Rio das Velhas Greenstone Belt, we propose that low δ¹³C_org (<?30‰) and dampened Δ³³S (0.4‰ to ?0.7‰) in banded iron formation reflect the marine diagenetic process of anaerobic methane oxidation. The overlying black shale (TOC up to 7.8%) with higher δ¹³C_org (?33.4‰ to ?19.2‰) and expanded Δ³³S (2.3‰ ± 0.8‰), recorded oxidative sulfur cycling that resulted in enhance preservation of S-MIF input from atmospheric sources of elemental sulfur. The sequence culminates in a metasandstone, where concomitant changes to more uniform δ¹³C_org (?30‰ to ?25‰), potentially associated with the RuBisCO I enzyme, and near-zero Δ³³S (?0.04‰ to 0.38‰) is mainly interpreted as evidence for local oxygen production. When placed in the context of other sequences worldwide, the Rio das Velhas helps differentiate the influences of global atmospheric chemistry and local marine diagenesis in Archean biogeochemical processes. Our data suggest that prokaryotic sulfur, iron, and methane cycles might have an underestimated role in pre-GOE sulfur minor isotope records.