青海东昆仑洪水河铁矿床新元古代含铁建造铁同位素特征及其成因意义

青海省东昆仑造山带洪水河铁矿床为一中型铁矿床,其含铁建造产于狼牙山组千枚岩中,矿石类型主要为块状磁铁石英岩型,少量为条带状磁铁石英岩型,前人一般认为其属于沉积变质型铁矿床。本文在前人研究基础上,对洪水河铁矿区含铁建造中块状铁矿石进行了铁同位素、主量元素、稀土元素和微量元素分析。结果显示：除1件样品外,其余含铁建造样品的铁同位素δ56FeIRMM014均介于0.97‰~1.97‰之间,和全球典型新元古代含铁建造的Fe同位素特征基本一致;铁矿石的SiO₂+Fe₂O₃质量分数高达78.56%~98.06%,具有极低的Al/(Al+Fe+Mn)值（0.00~0.06）,为典型的化学沉积岩;总稀土元素（w (∑REE)）变化范围为(16.49~80.89)×10^-6,没有明显的Ce异常(Ce/Ce*为0.93~1.05),轻稀土元素轻微亏损,显示出类似新元古代含铁建造型的特点。综合对比洪水河铁矿区含铁建造的Fe同位素组成、沉积时代和地球化学特征,推断洪水河铁矿区含铁建造的沉积环境为新元古代柴达木—东昆北陆块的被动大陆边缘构造环境,铁等成矿物质主要来源于海相热液流体;富含Fe²+的海相热液流体上涌并逐渐演变为低温热液后在亚氧化水体环境中与含氧海水混合,最后导致Fe²+被部分氧化并形成氢氧化铁,氢氧化铁逐渐沉积在大陆斜坡上最终形成含铁建造。洪水河铁矿的成因类型可划归为拉皮坦型新元古代含铁建造。     

鞍山-本溪地区条带状铁建造的铁同位素与稀土元素特征及其对成矿物质来源的指示

通过Fe同位素、稀土元素与主量元素相结合的方法,对辽宁省鞍山-本溪地区新太古代条带状铁建造(BIF)的成矿物质来源提出了有效制约.BIF的化学成分主要由TFe2O3和SiO2组成,并且具有较低的Al2O3和TiO2含量,表明该地区BIF型贫铁矿是由极少碎屑物质加入的化学沉积岩.稀土元素的总量较低,经页岩标准化后的稀土元素配分模式呈现轻稀土亏损、重稀土富集的特征,具有明显的Eu、Y、La正异常,这些特征表明该地区BIF是古海洋的化学沉积岩,同时具有明显的火山热液贡献特征.用多接收电感耦合等离子体质谱仪(MCICP-MS)测定Fe同位素的结果表明,相对于标准IRMM-014,所测样品均显示Fe的重同位素富集,且Fe同位素组成与Eu异常存在明显的正相关关系,表明该地区BIF中铁的来源与海底火山热液活动密切相关,首次从成矿元素Fe本身为条带状铁建造的成矿物质来源提供了直接的证据.     

河南舞阳经山寺铁矿床C-O-Si同位素成矿物质来源示踪

河南经山寺铁矿位于华北板块南缘,矿体形态为似层状、透镜状,铁建造以条带状铁矿石为主,含有少量的块状矿石,其顶底板围岩及矿体夹层主要为太华群铁山庙组大理岩。为探讨矿床成矿物质来源,对铁矿床进行碳、氧、硅同位素特征进行分析和研究,研究结果表明,矿化样品方解石的碳、氧同位素组成为δ13CV-PDB=-5.2‰~-1.4‰,δ18OV-SMOW=8.5‰~16.9‰,围岩大理岩样品方解石的碳、氧同位素组成为δ13CV-PDB=-1.0‰~1.6‰,δ18OV-SMOW=20.3‰~23.4‰,说明在成矿流体与围岩发生了水-岩反应,且流体与围岩发生了同位素交换,碳同位素组成主要由海相沉积碳酸盐岩经溶解作用提供的,且受中低温蚀变作用的影响,δ18OH2O组成值变化范围较大,指示热液体系可能为岩浆水和海水的混合热液。石英辉石磁铁矿矿石中石英的硅同位素组成为δ30SiNBS-28=-1.9‰~-0.4‰,围岩浅粒岩中硅同位素组成为δ30SiNBS-28=0‰,表明条带状铁建造中硅质来源于火山喷气作用,在变质成矿作用过程中硅同位素发生了动力学分馏作用,条带状铁建造中硅质沉淀造成δ30Si显示负值,综合分析认为,经山寺铁矿应属前寒武纪海底火山-沉积环境中热水化学沉积产物。     

广西三江地区富禄组条带状铁建造的铁同位素初步研究

在前寒武纪早期,条带状含铁建造(BIF)十分发育.然而,在1.8 Ga以后,BIF在地球上消失了,直到新元古代冰期,巴西、纳米比亚、澳大利亚和我国扬子地区又再次出现了BIF.     

安徽霍邱李老庄铁-菱镁矿床成因探讨:碳、氧同位素的指示意义北大核心CSCD

早前寒武纪李老庄铁-菱镁矿床位于华北克拉通南缘安徽霍邱铁矿带中部,赋存于火山-沉积变质岩系中,矿床内同时发育条带状磁铁矿(BIF)矿体和含铁菱镁矿体。为探讨菱镁矿的成因及其与BIF成矿的关系,针对磁铁矿-菱镁矿这一特殊成矿组合,对取自矿体岩芯的样品开展了显微岩相学观察、电子探针和C、O同位素分析研究。结果显示,矿床内与磁铁矿共生的菱镁矿和含铁菱镁矿矿石中的菱镁矿单矿物均含有较高含量的铁。李老庄矿床含铁菱镁矿矿石的δ^18O约为11‰,δ^13C为-2.16‰^-1.35‰;与磁铁矿共生的菱镁矿的δ^18O为12.49‰~15.43‰,δ^13C为-10.66‰^-5.30‰;矿区白云石大理岩的δ^18O为15.2‰~16.1‰,δ^13C为-2.57^-1.91‰,δ^13C与δ^18O呈同步降低。研究认为,该矿床是在形成富镁碳酸盐岩和BIF铁矿层的基础上,经低角闪岩相变质及富铁镁流体的蚀变交代,使成矿物质在赋矿围岩构成的向斜核部叠加富集形成的沉积-热液改造型矿床。     

云南省勐腊县曼洒菱铁矿床Fe同位素特征及其地质意义

首次研究了云南省勐腊县曼洒菱铁矿床碳酸盐岩层中菱铁矿的Fe同位素组成特征,并利用菱铁矿Fe同位素对矿床成因及成矿环境进行了制约。曼洒矿区菱铁矿δ~(56)Fe值变化范围为-0.337‰~-0.201‰,平均值为-0.261‰;δ~(57)Fe范围为-0.518‰~-0.289‰,平均值为-0.380‰。菱铁矿样品Fe同位素组成非常均一,富集铁的轻同位素。通过大量对比分析,提出曼洒铁矿床的成矿作用与海底热液活动有关,为含矿热水溶液喷溢出海底后快速堆积成矿,矿床形成于局限深水洼地的还原性环境。     

格陵兰伊苏亚铁矿床研究新进展

伊苏亚位于格陵兰岛西南努克市东北150km,条带状含铁建造(BIF)有9.61亿t资源量、铁平均质量分数36.48%。伊苏亚铁矿分布在3.8~3.7Ga的古太古代表壳岩带的东北方向。铁矿床赋存于变质火山岩系(绿岩系)和变质沉积岩的条带状含铁建造中。石英-磁铁矿型是已知6种条带状含铁建造中最主要的类型。条带状含铁建造中最常见的矿物组合是石英+磁铁矿+镁铁闪石(铁闪石)+阳起石+角闪石+方解石。根据元素地球化学特征、稳定同位素数据认为BIF是海底火山喷发及热液蚀变外加后期构造改造共同形成的。伊苏亚铁矿在勘探过程中广泛使用了航磁、航电、高光谱测量、航空辐射,重力等技术,在现有矿体的西南和东边地区预测出新的靶区。     

前寒武纪条带状硅铁建造的形成机制与地球早期的大气和海洋

前寒武纪条带状硅铁建造(BIFs)是地球早期特有的化学沉积建造类型,记录了当时大气和海洋的化学成分、氧化还原状态及演化。本文系统测定了华北地台条带状硅铁建造的硫硅氧同位素组成。不同时代和不同类型条带状硅铁建造中石英的硅同位素组成非常相似,强烈亏损30Si,δ30SiNBS-28大部分位于-2.0‰～-0.3‰之间,平均-0.8‰;硅铁建造中石英的δ18OV-SMOW相对较高,8.1‰～21.5‰,平均13.9‰;二者均与现代海底黑烟囱、泉华及热水沉积硅质岩的硅氧同位素组成相似。在同一样品中,磁铁矿条带中石英的δ30SiNBS-28普遍低于相邻硅质条带中石英的值,而δ18OV-SMOW刚好相反,反映了硅铁建造沉积时的初始特征。BIFs中硫化物的δ34SV-CDT变化范围很大,-22.0‰～+11.8‰,但大部分集中分布在0值附近。Δ33S=-0.89‰～+1.2‰,显示出了明显的硫同位素非质量分馏特征,说明当时大气氧浓度很低。与火山活动关系密切的Algoma型硅铁建造的Δ33S多为负值,而远离火山活动中心的Superior型硅铁建造的Δ33S多为正值。提出无论是Algoma型,还是Superior型BIFs都是由海底热液喷气作用形成的。富含溶解硅和铁的热水溶液喷发到在海底以后,由于温度突然下降,硅酸H4SiO4在海水中达到过饱和状态,导致SiO2首先沉淀,形成硅质层;随着热水溶液与海水的不断混合,温度不断降低,Eh值不断升高,Fe2+逐渐被氧化生成Fe3+随后沉淀,形成富铁层。一套硅铁韵律层代表了一次大的海底喷气活动;海底热液喷气的周期性活动形成了规律性的硅铁韵律层。BIFs的广泛分布和硫同位素非质量分馏效应的普遍存在,表明当时大气氧水平很低,可能不足现在氧水平的1‰;火山和海底喷气活动非常强烈,海水温度较高,呈酸性,pH值在3.0～5.5之间;海洋中可溶解硅H4SiO4和Fe2+的浓度很高;而可溶硫酸盐的浓度极低,1mM。早元古代(1.8Ga)以后海洋硫酸盐浓度升高,由富铁海洋转化为富硫酸盐的海洋,是造成BIFs消失的根本原因。大规模火山喷发和海底喷气活动对海洋的成分和氧化还原状态影响很大,使海洋的氧化时间较大气至少推迟了6亿年。     

绿片岩-低角闪岩相变质条件下磁铁铁矿与黄铁矿间的Fe同位素分馏

对辽宁省鞍山一本溪地区经历了绿片岩一低角闪岩相变质的新太古代条带状铁建造中磁铁矿和黄铁矿矿物对的Fe同位素分析结果显示:相对于标准IRMM-014,所有样品的磁铁矿和黄铁矿均显示Fe的重同位素富集;且黄铁矿的Fe同位素比值均大于磁铁矿的Fe同位素比值(ε57Fe黄铁矿ε57Fe磁铁矿),两种矿物的Fe同位素比值之差为△57Fe黄铁矿-磁铁矿=2.23～5.13.黄铁矿富集铁的重同位素表明矿物的Fe同位素组成并不代表其原始沉积的特征,而是在区域变质作用过程中Fe同位素发生了交换的结果.由同位素平衡判别图解可知,在绿片岩一低角闪岩相变质作用中,磁铁矿-黄铁矿间的Fe同位素基本达到了平衡,且在平衡条件下黄铁矿比磁铁矿更富集Fe的重同位素,二者之间的Fe同位素平衡分馏系数α黄铁矿-磁铁矿≈1.000 4‰±0.06‰(2σ).这一研究成果是对变质作用过程中Fe同位素的地球化学行为认识的重要进展.     

陕西南沙河地区车渡金矿床成因

针对陕西南沙河地区车渡金矿床进行了研究,研究结果表明,中—新元古界碧口群二亚群(Pt2-3bk2)中玄武质火山凝灰岩具Sr、Ba、Rb、Ce、P、Sm相对富集,Ta、Nb、Zr、Hf、Ti相对亏损的特征,显示钙碱性火山弧玄武岩的特点;车渡金矿床具有2种成因类型,一是与中生代逆冲推覆构造形成的韧性剪切带有关的强硅化蚀变岩型金矿,二是与中—新元古界碧口岩群二亚群火山凝灰岩有关的BIF型金矿。单颗粒磁铁矿成分分析认为,车渡含金磁铁石英岩中磁铁矿具有高的TFeO(平均值99.59%)含量和极低的TiO_2、MgO、A_(12)O_3、MnO含量,指示车渡磁铁石英岩金矿石中条带状磁铁矿属于沉积变质型成因条带状含铁建造。含金磁铁石英岩型金矿石的氢氧同位素显示,δ~(18)O_水值为12.34‰～12.45‰(平均值12.40‰),δD值为-112.6‰～-103.5‰(平均值-108.05‰),与鞍山—本溪地区条带状含铁建造型铁矿δD变化范围(-129‰～-75‰)一致,暗示车渡含金磁铁石英岩中石英矿物具有条带状含铁建造特征。     

Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite–carbonate–chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ⁵⁶Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ⁵⁶Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ⁵⁶Fe end member values are 0.4‰ for siderite and −0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ³⁰Si values that range between −1.0‰ and −2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate–chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite–carbonate–chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF’s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.     

冰川底部富铁溶液氧化沉淀:塔里木北缘新元古界库鲁克赛铁矿床的成因

新元古代沉积变质铁矿床是继大氧化事件(GOE)后,沉积间断10亿年(~1800 Ma至~750 Ma)之后,再次大规模出现的一种沉积铁建造类型。这类铁建造与新元古代冰碛岩密切伴生,是新元古代雪球地球事件的重要证据。文章选择与新元古代雪球地球事件有关的沉积变质赤铁矿床—库鲁克赛铁矿进行研究,通过锆石U-Pb定年和区域地层对比工作限定其形成时代为新元古代青白口纪末期—南华纪早期。锆石年龄谱值对比和岩相学研究表明,铁矿床中的碎屑物质主要来自于青白口系下部独断山组石英砂岩地层。主、微量元素研究表明,库鲁克赛铁矿形成于相对富氧或者从贫氧向富氧变化的环境,其成矿元素应主要与陆源物质风化有关,可能有少量成矿元素来自于低温海底热液或海水。笔者认为,库鲁克赛铁矿的形成与成冰纪冰水沉积作用有关,来自冰下水体、从冰下通道中流出的富铁缺氧水溶液与富氧的表层海水混合时,成矿元素快速氧化沉淀,胶结冰水中的近源砾石,进而形成了此种富铁砾岩型铁矿。     

Ancient geochemical cycling in the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal Craton

Variations in the isotopic composition of Fe in Late Archean to Early Proterozoic Banded Iron Formations (BIFs) from the Transvaal Supergroup, South Africa, span nearly the entire range yet measured on Earth, from –2.5 to +1.0‰ in ⁵⁶Fe/⁵⁴Fe ratios relative to the bulk Earth. With a current state-of-the-art precision of ±0.05‰ for the ⁵⁶Fe/⁵⁴Fe ratio, this range is 70 times analytical error, demonstrating that significant Fe isotope variations can be preserved in ancient rocks. Significant variation in Fe isotope compositions of rocks and minerals appears to be restricted to chemically precipitated sediments, and the range measured for BIFs stands in marked contrast to the isotopic homogeneity of igneous rocks, which have δ⁵⁶Fe=0.00±0.05‰, as well as the majority of modern loess, aerosols, riverine loads, marine sediments, and Proterozoic shales. The Fe isotope compositions of hematite, magnetite, Fe carbonate, and pyrite measured in BIFs appears to reflect a combination of (1) mineral-specific equilibrium isotope fractionation, (2) variations in the isotope compositions of the fluids from which they were precipitated, and (3) the effects of metabolic processing of Fe by bacteria. For minerals that may have been in isotopic equilibrium during initial precipitation or early diagenesis, the relative order of δ⁵⁶Fe values appears to decrease in the order magnetite > siderite > ankerite, similar to that estimated from spectroscopic data, although the measured isotopic differences are much smaller than those predicted at low temperature. In combination with on-going experimental determinations of equilibrium Fe isotope fractionation factors, the data for BIF minerals place additional constraints on the equilibrium Fe isotope fractionation factors for the system Fe(III)–Fe(II)–hematite–magnetite–Fe carbonate. δ⁵⁶Fe values for pyrite are the lowest yet measured for natural minerals, and stand in marked contrast to the high δ⁵⁶Fe values that are predicted from spectroscopic data. Some samples contain hematite and magnetite and have positive δ⁵⁶Fe values; these seem best explained through production of high ⁵⁶Fe/⁵⁴Fe reservoirs by photosynthetic Fe oxidation. It is not yet clear if the low δ⁵⁶Fe values measured for some oxides, as well as Fe carbonates, reflect biologic processes, or inorganic precipitation from low-δ⁵⁶Fe ferrous-Fe-rich fluids. However, the present results demonstrate the great potential for Fe isotopes in tracing the geochemical cycling of Fe, and highlight the need for an extensive experimental program for determining equilibrium Fe isotope fractionation factors for minerals and fluids that are pertinent to sedimentary environments.     

条带状铁建造:特征、成因及其对地球环境的制约

条带状铁建造(BIF)是由硅质和铁质组成的化学沉积岩,通常具有典型的薄层或薄板状构造。BIF不仅记录了丰富的岩石圈、大气圈、水圈和生物圈状态及演化的信息,而且与其相关的铁矿也是世界上最重要的铁矿资源类型。虽然对BIF的研究已取得了丰富的成果,近年来若干新颖的观点和重要的发现对进一步深入研究BIF成因提供了重要思考途径和研究线索。文章总结了BIF类型、矿物学和地球化学特征,分析了BIF形成条件及大规模缺失机理,阐述了BIF的形成和大气圈两次重大氧化事件(古元古代大氧化事件,2.4～2.1 Ga,新元古代氧化事件,0.8～0.55 Ga?)之间的关系,认为BIF与海底岩浆-热液活动具有密切的成因联系。最后,提出BIF的沉积和消亡与重大地质事件密切相关,这些重大地质事件也相互作用,共同制约着大气海洋环境演化、地球生物学和地球动力学过程。关于BIF精细成矿时代、条带/条纹形成的机制、重大地质事件对BIF形成的制约和BIF微生物成因等方面仍存在较多问题。随着大数据、精细成矿年代学、模拟实验、非传统稳定同位素(Fe、Cr、U、Mo和Cu同位素等)新技术方法的进步,及对现代洋底热液系统的深入认识,将有助于揭开BIF成因的神秘面纱。     

中国BIF型铁矿床地质特征和资源远景

BIF型铁矿床是中国最重要的铁矿床类型,占全国总查明资源储量55.2％.BIF型铁矿床主要分布在华北陆块,其次在扬子陆块.在华北陆块鞍山—本溪,密怀—冀东,五台—吕梁矿集区中铁矿床尤为集中,约占全国铁总探明储量41.5％.BIF型铁矿床在古太古代、中太古代、新太古代、古元古代和新元古代均有产出,但主要在新太古代—古元古...     

Organic Carbon Isotope Geochemistry of the Neoproterozoic Doushantuo Formation, South China

The Neoproterozoic Doushantuo Formation on the Yangtze Platform, South China, documents a sedimentary succession with different sedimentary facies from carbonate platform to slope and to deep sea basin, and hosts one of the world-class phosphorite deposits. In these strata, exquisitely preserved fossils have been discovered： the Weng＇an biota. This study presents carbon isotope geochemistry which is associated paired carbonate and organic matter from the Weng＇an section of a carbonate platform （shelf of the Yangtze Platform, Guizhou Province） from the Songtao section and Nanming section of a transition belt （slope of the Yangtze Platform, Guizhou Province） and from the Yanwutan section （basin area of the Yangtze Platform, Hunan Province）. Environmental variations and bio-events on the Yangtze Platform during the Late Neoproterozoic and their causal relationship are discussed. Negative carbon isotope values for carbonate and organic carbon （mean δ^13Corg = -35.0‰） from the uppermost Nantuo Formation are followed by an overall increase in δ^13C up-section. Carbon isotope values vary between -9.9‰ and 3.6‰ for carbonate and between -35.6‰ and -21.5‰ for organic carbon, respectively. Heavier δ^13Ccarb values suggest an increase in organic carbon burial, possibly related to increasing productivity （such as the Weng＇an biota）. The δ^13C values of the sediments from the Doushantuo Formation decreased from the platform via the slope to basin, reflecting a reduced environment with minor dissolved inorganic carbon possibly due to a lower primary productivity. It is deduced that the classical upwelling process, the stratification structure and the hydrothermal eruption are principally important mechanisms to interpret the carbon isotopic compositions of the sediments from the Doushantuo Formation.     

SHRIMP U–Pb zircon ages of tuffaceous mudrocks in the Brockman Iron Formation of the Hamersley Range,Western Australia

Tuffaceous mudrocks are common in the banded iron‐formations (BIF) of the Brockman Iron Formation. These tuffaceous mudrocks are either stilpnomelane‐rich or siliceous. Their compositions reflect bimodal volcanic activity in the vicinity of the Hamersley BIF depositional site. They also contain complex zircon populations that record resedimentation, syndepositional volcanism and post‐depositional isotopic disturbance. The best estimates of depositional age are obtained from siliceous tuffaceous mudrocks in the Joffre Member that contain 2459 ± 3 Ma and 2454 ± 3 Ma zircon populations most likely derived from felsic volcanism coeval with BIF deposition. These dates constrain the sedimentation rates for the ～370 m‐thick Joffre Member BIF to >15 m per million years. Siliceous tuffaceous mudrocks are not present in the underlying ～120 m‐thick Dales Gorge Member and it is uncertain whether previously reported ages of ca 2479–2470 Ma for this unit reflect detrital/xenocrystic or syndepositional zircon populations in resedimented stilpnomelane‐rich tuffaceous mudrocks. The increased abundance of tuffaceous mudrocks in the Joffre Member suggests that a pulse of enhanced igneous and hydrothermal activity accompanied deposition of the bulk of the Brockman Iron Formation BIF after ca 2460 Ma. This preceded and culminated in the emplacement of the 2449 ± 3 Ma large igneous province represented by BIF and igneous rocks of the Weeli Wolli Formation and Woongarra Rhyolite.     

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area, Guizhou Province, Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area, the Fe isotope compositions of riverine suspended particulates, lake suspended particulates, lake sediments, porewaters, phytoplanktons, and aerosols in the watersheds of Lake Aha (a mineralized water system) and Lake Hongfeng (a mesotrophic water system), which are located in the Karst area, southwest China, were investigated. The studied samples displayed a variable range between δ56Fe=?2.03‰ and 0.36‰. Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks. Fe isotope compositions of riverine Suspended Particulate Matter (SPM) were mainly affected by the types of tributaries. Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negative δ56Fe values (?0.89‰ to ?0.31‰) during summer, and there were significant increases of δ56Fe values in winter, except AR2, which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates, lake sediments, and porewaters. The epilimnetic particulate Fe of Lake Hongfeng had δ56Fe=?0.04‰ to 0.13‰, while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha, ranging from ?0.42‰ to ?0.09‰. Sediments collected from Hou Wu (HW) station of Lake Hongfeng have an average δ56Fe value of 0.09‰ and their corresponding porewaters have lighter Fe isotope compositions, ranging from ?0.57‰ to ?0.31‰; no significant variations have been observed. For the Liang Jiang Kou (LJK) station of Lake Aha, the content of reactive Fe and the concentration of sulfate were all high. Due to the reactive Fe recycling, including dissimilatory Fe reduction, adsorption, and Fe–sulfide formation, porewaters sampled near the sediment surface have been found to have a δ56Fe value as low as ?2.03‰ and an increase up to 0.12‰, with a burial depth of 10?cm. In contrast, an opposite variation trend was found for LJK sediments. Sediments sampled at 1-cm depth had a value of δ56Fe=?0.59‰ and decrease as low as ?1.75‰ with burial depth. This investigation demonstrated that significant Fe isotope fractionations occur in surface environments. Fe isotope compositions of particulate Fe were seriously affected by Fe sources, and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments, especially when there are significant amounts of reactive Fe and sulfate.     

Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ∼2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ³⁰Si between −1.3‰ and −0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ⁵⁶Fe values of −2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ⁵⁶Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ⁵⁶Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ¹³C values of ∼−10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ⁵⁶Fe of −0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe isotope signature. The long-term near-zero Fe isotope composition of the Hamersley and Transvaal BIFs is in balance with the assumed composition of the Fe sources. The negative Fe isotope composition of the investigated BIF samples, however, indicates either a perturbation of the steady state, or they have to be balanced spatially by deposition of isotopically heavy Fe. In the case of Si, the negative Si isotope signature of these BIFs stands in marked contrast to the assumed source composition. The deviation from potential source composition requires a complementary sink of isotopically heavy Si in order to maintain steady state in the basin. Perturbing the steady state by extraordinary hydrothermal activity or continental weathering in contrast would have led to precipitation of light Si isotopes from seawater. Combining an explanation for both elements, a likely scenario is a steady state ocean basin with two sinks. When all published Fe isotope records including BIFs, microbial carbonates, shales and sedimentary pyrites, are considered, a complementary sink for heavy Fe isotopes must have existed in Precambrian ocean basins. This Fe sink could have been pelagic sediments, which however are not preserved. For Si, such a complementary sink for heavy Si isotopes might have been provided by other chert deposits within the basin.