膏盐层在矽卡岩型铁矿成矿中的作用

矽卡岩型铁矿是我国富铁矿的重要类型,约占全国富铁矿总储量的60%。虽然膏盐层与矽卡岩型铁矿的关系已引起部分矿床学家的关注,但膏盐层的控矿机制尚不清楚。本文以我国最重要的大冶式和邯邢式矽卡岩型铁矿为例,探讨了膏盐层在矽卡岩型铁矿成矿中的作用。膏盐层富含碳酸盐、石膏和石盐等,不仅可以为成矿提供大量Na⁺、Cl^-、CO3²⁺等矿化剂,使围岩发生钠长石化、方柱石化（氯化）和矽卡岩化等蚀变,使Fe²⁺以NaFe-Cl等络合物形式搬运,膏盐层还是地壳深处最重要的氧化障,能够将硅酸盐熔体和成矿溶液中的Fe²⁺氧化成Fe³⁺,富集形成铁矿床,是矽卡岩型铁矿成矿的关键因素。大冶地区的膏盐层属于中三叠统下部的嘉陵江组,邯邢地区的膏盐层属于中奥陶统马家沟组—峰峰组。大冶和邯邢式矽卡岩型铁矿中硫化物的δ³⁴S_V-CDT值异常高,计算结果表明矿床中约80%的硫来自膏盐层硫酸盐的还原,还原温度多在500℃以上,但硫化物的沉淀温度相对较低,就位时间稍晚;硫酸盐的δ³⁴S_V-CDT值和还原温度越高,硫化物的δ³⁴S_V-CDT值越高,原始岩浆硫所占比例越高,硫化物的δ³⁴S_V-CDT值越低。当炽热的岩浆与膏盐层（CaSO₄）发生同化混染时,SO₄^2-将硅酸盐熔体中的Fe²⁺氧化成Fe³⁺,Fe³⁺无法进入硅酸盐矿物晶格,而形成Fe₃O₄/Fe₂O₃进入熔体,铁氧化物在磷、氯化钠、水等挥发分和盐类物质的作用下在岩浆房中与硅酸盐熔体发生不混熔,形成铁矿浆,沿构造有利部位贯入,形成矿浆型铁矿床。在矽卡岩型铁矿床中,矿浆充填型和热液交代型矿体同时存在,二者在空间上具有一定的分带性,有时渐变过渡,矿浆充填型铁矿体通常位于深部靠近成矿岩体的部位,而热液交代型铁矿体位于成矿流体运移的前方。在SO₄^2-氧化Fe²⁺的同时自身被还原为S^2-,与Fe²⁺结合形成硫铁矿,分布在铁矿的上部或边部。     

华北中元古代浅海碳酸盐沉淀方式变化:海水氧化还原条件波动的响应?*

海相碳酸盐的沉淀方式被认为与水体氧化还原条件密切相关,即太古宙至古元古代缺氧的铁化海水中碳酸盐沉淀抑制剂Fe²⁺和Mn²⁺强力抑制灰泥在水柱中成核,但允许文石直接在海底生长,从而导致大量文石以海底沉淀方式产出,而新元古代适度的氧化海水则有利于灰泥以水柱沉淀方式形成。然而,碳酸盐沉淀方式的长期变化还可能受控于其他因素,其与海水氧化还原条件之间的关系还需要通过大量具体实例来验证。针对上述科学问题,笔者选择碳酸盐沉淀方式尚处于过渡时期的华北中元古界碳酸盐岩为研究对象,开展碳酸盐沉淀方式及与之对应的氧化还原条件研究。结果表明,华北高于庄组三段(约1.56 Ga)、雾迷山组四段下部(约1.48 Ga)和铁岭组二段(约1.44 Ga)发育大量灰泥水柱沉淀,其Ⅰ/(Ca+Mg)值较高(普遍大于0.5 μmol/mol)、Ce负异常(低至0.8),指示适度氧化的条件;而高于庄组四段下部(约1.55 Ga)和雾迷山组二段中部(约1.50 Ga)则发育大量纤维状文石海底沉淀,其Ⅰ/(Ca+Mg)值约为0,指示次氧化至缺氧的环境。因此,本研究首次用大量实例证实了前寒武纪海水氧化还原条件对碳酸盐沉淀方式的重要调控作用,并且后者可作为海水氧化还原条件分析的重要指标,适用于高效开展长序列、多剖面的低氧背景下前寒武纪碳酸盐岩地层的氧化还原条件分析。     

华北中元古代鱼骨状方解石: 成因机制和古环境意义*

鱼骨状方解石是一种特殊的碳酸盐沉积,由锯齿状亮暗交互的亚毫米级条带组成,主要见于太古宙。以往认为,鱼骨状方解石属无机化学沉淀成因,形成于水体缺氧、碳酸盐过饱和、富Fe²⁺、Mn²⁺等碳酸盐沉淀抑制剂的环境条件;在地质记录中其丰度随时间的减少反映了海洋的长期氧化趋势。文中首次在华北地台中元古界高于庄组四段微生物礁内发现了大量鱼骨状方解石。宏观观察表明,这些鱼骨状方解石主要以微生物礁孔洞充填物形式产出,明显区别于太古宙以海底沉淀形式直接产出在海底的鱼骨状方解石。显微研究发现,鱼骨状方解石晶体纤维具有沿晶体生长方向旋转消光特征,证明其内部亚晶的光学C轴从纤维底部的随机排列逐步旋转至上部垂直纤维生长方向。这符合球状晶体生长模式,需要方解石沉淀抑制剂的参与。鱼骨状方解石产出具有丰度随时间减少以及产出形式由海底沉淀向孔洞胶结物转变的特征。这些特征与海洋氧化逐渐增强以及具氧化还原敏感属性的碳酸盐沉淀抑制剂逐渐从水体中移除相吻合。笔者认为鱼骨状方解石的沉淀抑制剂为Fe²⁺和Mn²⁺,这与微生物岩无明显Ce异常和Fe²⁺极强的抑制能力相一致。因此,鱼骨状方解石可用于指示缺氧环境条件。此外,显微和超微研究也表明鱼骨状方解石晶体内存在有大量与其生长方向一致的菌丝体残余和与之密切伴生的有机矿物,表明微生物为鱼骨状方解石成核和初始沉淀提供了重要垫板。     

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。     

沉积变质型铁矿成矿条件及富铁矿形成机制

我国铁矿床类型有沉积变质型、岩浆型、接触交代 热液型(矽卡岩型)、火山岩型、沉积型和风化淋滤型6种,以沉积变质型最为重要。我国的沉积变质型铁矿床主要分布于华北克拉通,以鞍山式铁矿为代表,沉积时代为新太古代末,为阿尔果马型条带状铁建造 (BIF)变质而成;吕梁地区的袁家村式铁矿为苏比利尔型BIF变质而成,BIF沉积时代为2. 384~2. 210 Ga或新太古代末;舞阳、霍邱地区的沉积变质型铁矿可能为苏比利尔型BIF变质产物,BIF沉积时代分别为2. 473~2. 468 Ga、＜2. 54 Ga。BIF的形成与缺氧环境向大氧化事件初期的层化海洋环境过渡有关,海水中巨量溶解的铁质部分氧化,在初始层化海洋氧化还原界面附近的浅海环境以胶体形式沉淀。我国的BIF遭受区域变质变形作用,成为条带状磁铁石英岩,作为沉积变质型铁矿开发利用。BIF经历后期流体改造可形成富铁矿,形成机制有“去硅富铁”、“铁质活化再富集”和“去碳酸盐富铁”3种,弓长岭富铁矿的成矿年龄为1. 85 Ga左右,由BIF“去硅富铁”而成;齐大山富铁矿可能形成于2. 5 Ga,由BIF“铁质活化再富集”而成;袁家村富铁矿形成于1. 41~1. 34 Ga,可能由含碳酸盐的BIF“去碳酸盐富铁”而成。     

辽宁本溪贾家堡子地区BIF铁矿床地球化学特征

利用主量元素和稀土元素相结合的地球化学方法,对本溪贾家堡子铁矿成矿物质来源和矿床成因进行了研究.结果表明：贾家堡子地区条带状铁矿（BIF）的化学成分主要为TFe₂O₃和SiO₂,并且Al₂O₃和TiO₂含量较低,这一特征与鞍本地区及山西五台山和冀东迁安地区条带状铁矿基本一致,指示该条带状铁矿是由极少碎屑物质加入的化学沉积岩.稀土元素呈现弱轻稀土亏损、重稀土富集的特征,具有明显的Eu正异常特征,表明该BIF的稀土元素来源于火山热液和海水的混合液.贾家堡子地区条带状铁矿床成因类型为Algoma型铁矿.     

国内外前寒武纪条带状铁建造研究现状

条带状铁建造(BIFs)主要发育于早前寒武纪时期(3.8~1.8Ga),记录了早期地球演化的重要信息且蕴含丰富的铁矿石资源。本文梳理总结了国内外BIF相关领域的研究认识及存在问题:1统计对比显示,BIF沉积事件与地幔柱、地壳增生等重大地质事件相关;2稀土元素及Nd同位素示踪表明,Fe来源于海水与海底高温热液的混合溶液,其中高温热液与海水比例为1:1000;3 BIFs缺乏负Ce异常且富集重Fe同位素,暗示沉积时古海洋整体处于缺氧环境以避免Fe~(2+)发生氧化;4一些重要科学问题尚未解决,例如Si的主要来源、沉淀机制及条带成因等;5华北克拉通BIFs多形成于约2.54Ga,BIF类型、形成时代与富矿成因等问题有待深入研究。本文认为,加强国内外典型BIFs的对比研究并适当应用现代先进测试技术,有利于探索BIF沉积的精细过程及古老克拉通的早期演化。     

华北克拉通前寒武纪BIF铁矿研究:进展与问题

研究表明,BIF铁矿在华北克拉通的分布具有一定规律性.大规模BIF铁矿主要发育在绿岩带分布区的鞍山-本溪、冀东、霍邱-舞阳、五台、鲁西和固阳等地;华北克拉通时代最古老的BIF形成于古太古代,最年轻BIF形成于古元古代早期,但BIF铁矿的峰期为新太古代晚期(2.52 ～2.56Ga);BIF铁矿类型可划分为阿尔戈马型和苏比利尔湖型两类,但华北以晚太古代绿岩带中的阿尔戈马型为主,仅吕梁的古元古代袁家村铁矿具典型苏比利尔湖型铁矿特征.根据BIF在绿岩带序列中的产出部位和岩石组合关系,可将华北BIF划分为:1)斜长角闪岩(夹角闪斜长片麻岩)-磁铁石英岩组合;2)斜长角闪岩-黑云变粒岩-云母石英片岩-磁铁石英岩组合;3)黑云变粒岩(夹黑云石英片岩)-磁铁石英岩组合;4)黑云变粒岩-绢云绿泥片岩-黑云石英片岩-磁铁石英岩组合;5)斜长角闪岩(片麻岩)-大理岩-磁铁石英岩组合等5种类型.华北克拉通BIF形成时代与早前寒武纪岩浆活动的时间基本一致(2.5～2.6Ga),但与华北克拉通陆壳增生的峰期(2.7～2.9Ga)有一定偏差,其原因可能与新太古代晚期华北克拉通构造-热事件十分强烈有关.华北克拉通新太古代BIF大多形成于岛弧环境,但局部地区(如固阳)BIF铁矿可能形成于深部有地幔柱叠加的岛弧环境.华北克拉通BIF富矿主要有三种类型:原始沉积、受后期构造-热液叠加改造和古风化壳等,但总体不发育富铁矿,国外发育的风化壳型富铁在我国甚为少见.本文认为在探讨BIF铁矿类型时,需要从绿岩带发育序列进行综合判别.阿尔戈马型铁矿一般产于克拉通基底(绿岩带)环境,苏比利尔湖型铁矿一般形成于稳定克拉通上的海相沉积盆地或被动大陆边缘.华北克拉通BIF铁矿地球化学研究结果表明,BIF铁矿无Ce负异常且Fe同位素为正值,从而暗示铁矿沉淀的环境为低氧或缺氧环境,而铕正异常可能指示BIFs为热水沉积成因,其机制可能为海水对流循环从新生镁铁质-超镁铁质洋壳中淋滤出F(e)和Si等元素,在海底排泄沉淀成矿,而条带状构造的形成可能归咎于成矿流体的脉动式喷溢.但对于BIF铁矿的物质来源、成矿条件和机制、富铁矿成因、华北克拉通不发育苏比利尔湖型铁矿的原因等方面,仍需深入研究.     

新疆西天山式可布台铁矿地质特征及成因分析

式可布台铁矿床位于新疆西天山阿吾拉勒成矿带西段,其矿体形态呈似层状、层状及透镜状,顺层产出于上石炭统伊什基里克组中。矿石矿物以赤铁矿为主,含少量菱铁矿,脉石矿物主要为铁碧玉和石英。矿石呈自形-半自形粒状、细晶质结构,致密块状和条带状构造。在显微观察的基础上,重点对矿石进行了主量和微量元素及电子探针分析。结果表明,矿石中赤铁矿电子探针数据在(Ti+V)-(Ca+Al+Mn)图的投点落于BIF区域内及其附近,表明其形成过程与BIF相似,菱铁矿电子探针数据MnO含量大于0.5%,说明其为沉积成因;矿石稀土元素具明显的Eu正异常(δEu=1.16～5.16)、高(Sm/Yb)PAAS值及近似的海底热液Y/Ho值(Y/Ho=23.0),均表明成矿物质来源与海底热液有关;矿石主量元素中高的MnO/TiO_2值(4.33～49.36)及缺乏强烈的负Ce异常(δCe=0.63～0.85),表明其沉积环境远离陆缘,海水的氧化还原状态为氧化-低氧化的过渡环境。综合研究表明,式可布台铁矿物质来源主要与海底热液有关,赤铁矿为氧化-低氧条件下海水的化学沉积成因,成岩过程中在有机质参与下菱铁矿由赤铁矿转换而形成。     

印度达尔瓦尔克拉通绿岩带BIF型铁矿地质特征及成因分析

印度铁矿储量约占全球的7%,矿石类型以前寒武纪BIF铁矿为主,其中产于绿岩带以及绿片岩相岩石中的BIF型铁矿是印度最重要的铁矿类型。南印度地盾达尔瓦尔克拉通发育众多绿岩带,绿岩带中发育大规模BIF铁矿,BIF铁矿属于不同的地层序列,有不同的岩石组合关系。笔者对吉德勒杜尔加绿岩带和库斯赫塔吉绿岩带BIF地球化学分析表明,根据Al_2O_3含量,BIF分为页岩BIF(Al_2O_3≥2%)和石英岩BIF(Al_2O_3≤2%),BIF呈石英氧化物相,碳酸盐相和硫化物相BIF主量和微量元素表明BIF为陆源碎屑沉积和火山碎屑沉积共同作用形成;稀土元素表明BIF铁矿呈Ce负异常和Eu正异常。达尔瓦尔克拉通测年数据表明,经过2.7~2.65Ga和2.58~2.54Ga两期主要的火山作用,2.7~2.6Ga和2.58~2.52Ga2个阶段的大陆增生作用,形成了达尔瓦尔克拉通和绿岩带。BIF成矿来源上,AMOR的高温热液提供大量的Fe和SiO_2,海洋中生物光合作用提供了O_2,在化学沉积和碎屑沉积共同作用下,形成了BIF铁矿。     

浅谈前寒武纪条带状铁建造的沉积-变质成矿过程

条带状铁建造(BIF)是3.5~1.8Ga前陆架和洋盆的常见沉积物。前寒武纪条带状铁建造构成了世界上重要的铁矿资源。虽然它们成矿过程及其演化的许多方面的问题仍未解决,但人们普遍认为,它们沉积方式的长期变化与地球的环境和地球化学演化有关。条带状铁建造记录了前寒武纪古海洋、古环境、大气条件和细菌代谢条件以及铁的来源和沉积过程。大型BIF沉积与大火成岩省有成因联系,其铁的来源与火山物质加入的海底热液体系有关,或有陆缘岩石风化的无机物产物加入,越靠近陆缘,陆源碎屑物质加入的越多。然而,在太古宙到古元古代期间,BIF沉积的深水盆地中陆源物质的加入很少。那时的铁建造沉积在缺氧的海洋中,通过微生物的光合作用、无氧光合氧化和紫外光线辐射氧化等机制对溶解的二价铁进行氧化,从而形成三价铁氢氧化物和氧化物的沉积。大多数BIF大型矿床,自其在沉积环境中形成以来,它们在从太古宙直至中生代的漫长的地质历史演化过程中经历了铁矿的品位由低到高转化的复杂地质过程,一般经历了深部交代变质作用的除硅、除碳酸岩矿物的富集成矿和浅部风化富集成矿过程。许多BIF铁矿经历了从绿片岩相到角闪岩相变质作用,但到达的压力条件都不是很高,这或许与俯冲的高密度BIF铁矿难以折返的动力学机制有关。迄今为止,变质作用、尤其是高级变质作用对成矿过程的影响研究较少,是今后值得关注的领域。     

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。     

Changes of Ge/Si,REE + Y and SmNd isotopes in alternating Fe- and Si-rich mesobands reveal source heterogeneity of the ~ 2.54 Ga Sijiaying banded iron formation in Eastern Hebei,China

The North China Craton (NCC) is one of the most important regions hosting abundant banded iron formations (BIFs). The ~ 2.54 Ga Sijiaying BIF, the best-preserved and most extensive deposit in Eastern Hebei, is intercalated and closely associated with meta-volcanic rocks of the Luanxian Group. In this context, major and trace element and SmNd isotopic analyses of individual mesobands of a Sijiaying BIF specimen were conducted to characterize the source and depositional environment over a transient period.Low Al₂O₃, TiO₂ and high field strength elements (HFSEs) concentrations show that the BIF is relatively detritus-free. Shale-normalized rare earth and yttrium distributions (REE + Y) of individual BIF mesobands exhibit positive La anomalies, enrichment in HREE relative to LREE and MREE and suprachondritic Y/Ho ratios, which are typical features of marine waters throughout the Archean and Proterozoic. The presence of consistently positive Eu anomalies indicates a significant high-T hydrothermal input, while the absence of true Ce anomalies suggests deposition from an anoxic water column. By comparison with other typical BIFs (e.g., the Isua BIF from Greenland; the Kuruman BIF from South Africa), the Sijiaying BIF is depleted in HREE, and appears to record variations in solute fluxes related to changing intensities of hydrothermal activity. These features, coupled with SmNd isotopic relations and Ge/Si distributional patterns, point to two decoupled sources controlling the depositional environment of the BIF and thus reveal source heterogeneity for silica and iron of the Sijiaying BIF. High Fe fluxes were associated with seafloor-vented hydrothermal fluids, which received their SmNd isotopic signature from alteration of depleted oceanic crust; whereas significant amounts of silica were associated with ambient seawater whose REE signature was controlled by solutes derived from weathering of nearby Mesoarchean continental landmasses. The old (up to ~ 3.0 Ga) Nd (T_DM) model ages of Si-rich mesobands of the BIF support such a scenario.     

冀东、五台和吕梁地区条带状铁矿的稀土元素特征及其地质意义

详细报道了冀东、五台和吕梁地区条带状铁矿全岩样品的稀土元素分析结果。结果表明,研究区BIF具有非常相似的特征：稀土总量均较低;经页岩标准化的稀土元素配分模式均呈现轻稀土亏损、重稀土富集的特征;Y/Ho比值较高;具有明显的Eu、Y、La的正异常,且这些特征表明研究区BIF的稀土元素来源于火山热液和海水的混合溶液。虽然BIF均显示Eu正异常,但不同类型、不同沉积年龄BIF的铕异常程度不同：与吕梁地区Superior型铁矿相比,冀东和五台地区的Algoma型铁矿显示了更大的Eu正异常;并且自中太古代-新太古代-古元古代,BIF的铕正异常逐渐减小,这可能反映了随着BIF沉积年龄的减小,进入到该地区海水中的高温热液流体逐渐减少;同时,研究区BIF缺乏明显的Ce负异常,可能暗示在BIF沉积时海水的氧化还原状态为缺氧环境。     

Neoproterozoic banded iron formations

Two epochs of the formation of ferruginous quartzites—Archean-Paleoproterozoic (3.2–1.8 Ga) and Neoproterozoic (0.85–0.7 Ga)—are distinguished in the Precambrian. They are incommensurable in scale: the Paleoproterozoic Kursk Group of the Kursk Magnetic Anomaly (KMA) extends over 1500 km, whereas the extension of Neoproterozoic banded iron formations (BIF) beds does not exceed a few tens of kilometers. Their thickness is up to 200 m and not more than 10 m, respectively. The oldest BIFs are located in old platforms, whereas Neoproterozoic BIFs are mainly confined to Phanerozoic orogenic (mobile) zones. Neoproterozoic BIFs universally associate with glacial deposits and their beds include glacial dropstones. In places, they underlie tillites of the Laplandian (Marinoan) glaciation (635 Ma), but they are more often sandwiched between glaciogenic sequences of the Laplandian and preceding Sturtian or Rapitan glaciation (730–750 Ma). Neoproterozoic BIFs are rather diverse in terms of lithology due to variation in the grade of metamorphism from place to place from low grades of the greenschist facies up to the granulite facies. Correspondingly, the ore component is mainly represented by hematite or magnetite. The REE distribution and (Co + Ni + Cu) index suggest an influence of hydrothermal sources of Fe, although it was subordinate to the continental washout. Iron was accumulated in seawater during glaciations, whereas iron mineralization took place at the earliest stages of postglacial transgressions.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

Geochemical Constraints on the Origin of Banded Iron Formation‐Hosted Iron Ore from the Archaean Ntem Complex (Congo Craton) in the Meyomessi Area,Southern Cameroon

Banded iron formations (BIFs) are the most significant source of iron in the world. In this study, we report petrographic and geochemical data of the BIF from the Meyomessi area in the Ntem Complex, southern Cameroon, and discuss their genesis and the iron enrichment process. Field investigations and petrography have revealed that the studied BIF samples are hard; compact; weakly weathered; and composed of magnetite, subordinate quartz, and geothite. The geochemical composition of the whole rock reveals that iron and silica represent more than 98 wt% of the average composition, whereas Al₂O₃, TiO₂, and high‐field strength elements (HFSE) contents are very low, similar to detritus‐free marine chemical precipitates. The total iron (TFe) contents range from 48.71 to 65.32 wt % (average of 53.29 wt %) and, together with the low concentrations of deleterious elements (0.19 wt % P on average), are consistent with medium‐grade iron ores by global standards. This interpretation is confirmed by the SiO₂/Fe₂O_3total versus (MgO + CaO + MnO)/Fe₂O_3total discrimination plot in which most of the Meyomessi BIF samples fall in the field of medium‐grade siliceous ore. Only one sample (MGT94) plots in the high‐grade magnetite–geothite ore domain. The high Fe/Ti (376.36), Fe/Al (99.90), and Si/Al (29.26) ratios of the sample are consistent with significant hydrothermal components. The rare earth elements (REE) contents of the studied BIF samples are very low (∑REE: 0.81–1.47 ppm), and the Post‐Archaean Australian Shale (PAAS)‐normalized patterns display weak positive Eu anomalies (Eu/Eu*: 1.15–1.33), suggesting a syngenetic low‐temperature hydrothermal solutions, similar to other BIF worldwide. However, the Meyomessi BIFs show high Fe contents when compared to the other BIFs. This indicates an epigenetic mineralization process affected the Meyomessi BIF. From the above results and based on the field and analytical data, we propose that the genetic model of iron ores at the Meyomessi area involves two stages of the enrichment process, hypogene enrichment of BIF protore by metamorphic and magmatic fluids followed by supergene alteration as indicated by the presence of goethite in the rocks.     

SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ¹⁸O range from +7.9‰ to +27.5‰ and include the highest reported δ¹⁸O values for BIF quartz. Values of δ³⁰Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ³⁰Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ¹⁸O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ³⁰Si up to 3‰, similar to the range in δ³⁰Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ³⁰Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ³⁰Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ³⁰Si < −0.5‰) but silicon from continental weathering (δ³⁰Si ∼ 1‰) was an important source as early as 3.8 Ga.