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.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

安徽霍邱BIF铁矿地球化学特征及其成矿意义：以班台子和周油坊矿床为例

安徽霍邱铁矿田位于华北克拉通南缘,是一个大型BIF铁矿田.本文对霍邱矿田班台子矿区和周油坊矿区的铁矿石及其赋存的岩石共28件样品进行了详细的主微量元素地球化学分析.分析结果表明,班台子矿区的片麻岩和角闪岩的原岩属于一套亚碱性系列的岩石,具有大离子亲石元素(LILE)富集,高场强元素(HFSE)明显亏损的火山弧岩石的特征.班台子角闪岩具有低的K2O含量和Ti/V值,Ti/V=22.7 ～ 25.9,平均24.5,与岛弧拉斑玄武岩一致.弧后盆地玄武岩化学组成具有类似岛孤拉斑玄武岩的特征.BIFs的形成往往需要构造稳定的半深水-深水盆地,孤后盆地能够为BIFs韵律条带的产生提供稳定的沉积环境,因此霍邱BIFs铁矿的大量出现说明班台子矿区角闪岩形成于弧后盆地,代表了霍邱铁矿形成的构造环境.班台子矿区铁矿石的(Eu/Eu*)SN=1.57 ～1.82,与Superior型(简称S型)BIFs特征一致;而周油坊矿区假象镜铁矿的(Eu/Eu*)SN=1.93 ～3.41,与Algoma型(简称A型)BIFs特征比较吻合.正Eu异常的强弱反应了成矿位置距离海底火山热液喷气口的远近.因此,我们推断霍邱地区BIFs型铁矿形成位置与海底火山热液喷气口的距离比较特别,处于A型向S型过渡的位置.角闪岩和片麻岩及其赋存的铁矿石的Al2O3和TiO2良好的线性相关性说明铁矿石铁质部分来源于侵蚀的弧后盆地玄武岩.Y/Ho比值=31.05 ～56.67,平均为46.65,说明霍邱铁矿继承了海水与热液的混合特征,其中,海水的贡献更大一些.周油坊矿区的大理岩主要化学组成CaO为28.49％ ～29.10％,MgO为20.25％ ～ 21.22％以及少量的SiO2(2.45％～6.10％).与平均显生宙石灰岩相比,周油坊大理岩亏损LILE和HFSE;与后太古代平均澳大利亚页岩(PAAS)相比,周油坊假象镜铁矿稀土元素总量低,明显正Eu异常,Ce无明显异常,Y/Ho比值介于35.00～56.67,平均48.81.这些特征显示大理岩及其赋存的假象镜铁矿形成于缺氧的海洋环境,海水中的氧能使亚铁离子氧化成三价铁离子沉淀出Fe(OH)3,但不足以使Ce3+氧化成Ce4+.     

Petrology and Geochemistry of the Banded Iron Formation of the Kuluketage Block,Xinjiang, NW China: Implication for BIF Depositional Setting

The Kuluketage block, located in the northeast Tarim craton, is one of the largest Precambrian blocks in the Xinjiang province. Recently, many banded iron formation (BIF)‐type (Superior‐type) deposits have been discovered in the western part of the Kuluketage block. These deposits occurred in the Paleoproterozoic Shayiti Formation, Xingditage Group, which has a nearly E–W distribution in the southern Xinger and Xingdi faults. Tremolite biotite schist and quartzite are the main wall rocks. The geochemical characteristics of schist indicate that the BIFs occurred in a passive continental margin environment. The LA–ICP–MS zircon ²⁰⁶Pb/²³⁸U ages of BIF and late syenite are 1945 ± 10 Ma(MSWD = 0.77) (weighted average age) and 1974 ± 27 Ma(MSWD = 1.05) (upper intercept age), respectively, indicating that the BIFs occurred in the Paleoproterozoic. In addition, the approximately 1.9 Ga magmatic and metamorphic events are consistent with the global‐scale 2.1–1.8 Ga collisional orogen events which are associated with the assembly of the Columbia supercontinent. The geochemical characteristics show that magnetite and quartz are dominant components (total content, 91.65–98.22 wt.%), and the Zr(Nb) and TiO₂, Zr(Nb) and Al₂O₃ and Zr and Y/Ho display strongly positive correlations, illustrating the addition of crustal materials into the chemical precipitate of the original BIFs. The higher Zr, Nb and Al₂O₃ contents and a lower Y/Ho ratio of the Kuluketage BIFs indicate a higher terrigenous detrital component contaminant compared to BIFs of North China Craton (NCC). The rare earth and yttrium (REY) distribution patterns show a slight LREE enrichment and weak Eu positive anomaly features, indicating that the source of Fe and Si of the Kuluketage BIFs is mainly from the contribution of low‐temperature hydrothermal alteration of the oceanic crust. In addition, along with the decreasing BIF depositional age, the declining of Eu anomaly values reflects the increasing importance of low‐temperature hydrothermal solutions relative to high‐temperature hydrothermal solutions. Moreover, no Ce anomalies in studied BIFs, NCC and Xinyu BIFs are attributed to relative reducing environmental condition when the original BIFs precipitated.     

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.     

Metal cycling in Mesoproterozoic microbial habitats: Insights from trace elements and stable Cd isotopes in stromatolites

Reconstructing the environmental conditions that supported early life on Earth relies on well-preserved geochemical archives in the rock record. However, many geochemical tracers either lack specificity or they are affected by post-depositional alteration. We present a data set of major and trace element abundances and Cd isotope compositions of dome-shaped and conophyton-type stromatolites of the Late Mesoproterozoic Paranoá Group (Brazil), showing distinct values with unprecedented resolution at the lamina scale.The studied stromatolites consist of dolomite with a high purity and a negligible content of immobile elements (e.g., <0.66 ppm Zr), indicating that elemental compositions are not influenced by detrital contamination. Even though the carbonates have experienced different extent of recrystallization, the measured elemental and isotopic compositions do not correlate with fluid mobile elements. The stromatolites thus represent prime archives for geochemical proxies to reconstruct paleo-environmental conditions.Two endmember compositions can be distinguished by multiple proxy analysis, reflecting the contrasting depositional environments of the two types of stromatolites: Shale-normalized rare earth elements including yttrium (REY_SN) patterns of domal stromatolites show a light REY_SN (LREY) enrichment (Yb_SN/Pr_SN < 0.84), slightly super-chondritic Y/Ho ratios (33.6–39.3) and unfractionated Cd isotopes relative to upper continental crust. This indicates that the stromatolites formed in a shallow-water environment that was episodically influenced by seawater. Their REY and Cd compositions are dominated by dissolved elements that were delivered via weathering and erosion processes from the ambient continent.In contrast, REY_SN patterns of the conophyta are parallel those of modern seawater with an LREY_SN depletion relative to HREY_SN (Yb_SN/Pr_SN = 2.1 to 3.9), positive Gd_SN anomalies (1.1 to 1.4) and strong super-chondritic Y/Ho ratios (37.9 to 46.2), suggesting a microbial habitat that was dominated by seawater. Cd isotopes correlate negatively with Cd and U, but positively with Mn and Ce concentrations, reflecting authigenic carbonate formation at different depths within a redox gradient of the ancient microbial mat. ε^112/110Cd_dol values increase from −3.52 at the mat surface to +3.46 in the interior of the mat, due to the effect of kinetic fractionation during Cd-uptake, e.g. by adsorption onto organic matter or by precipitation of sulfides, in addition to incorporation into carbonate minerals. Hence, our multi-proxy approach including Cd isotopes bears a high potential to shed light on environmental conditions in ancient microbial habitats and the activity of microbial life on Early Earth.     

Seawater-like trace element signatures (REE + Y) of Eoarchaean chemical sedimentary rocks from southern West Greenland,and their corruption during high-grade metamorphism

Modern chemical sediments display a distinctive rare earth element + yttrium (REE + Y) pattern involving depleted LREE, positive La/La*_SN, Eu/Eu*_SN, and Y_SN anomalies (SN = shale normalised) that is related to precipitation from circumneutral to high pH waters with solution complexation of the REEs dominated by carbonate ions. This is often interpreted as reflecting precipitation from surface waters (usually marine). The oldest broadly accepted chemical sediments are c. 3,700 Ma amphibolite facies banded iron-formation (BIF) units in the Isua supracrustal belt, Greenland. Isua BIFs, including the BIF international reference material IF-G are generally considered to be seawater precipitates, and display these REE + Y patterns (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004). Greenland Eoarchaean BIF metamorphosed up to granulite facies from several localities in the vicinity of Akilia (island), display REE + Y patterns identical to Isua BIF, consistent with an origin by chemical sedimentation from seawater and a paucity of clastic input. Furthermore, the much-debated magnetite-bearing siliceous unit of “earliest life” rocks (sample G91/26) from Akilia has the same REE + Y pattern. This suggests that sample G91/26 is also a chemical sediment, contrary to previous assertions (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004), and including suggestions that the Akilia unit containing G91/26 consists entirely of silica-penetrated, metasomatised, mafic rock (Fedo and Whitehouse 2002a). Integration of our trace element data with those of Bolhar et al. (Earth Planet Sci Lett 222:43–60, 2004) demonstrates that Eoarchaean siliceous rocks in Greenland, with ages from 3.6 to 3.85 Ga, have diverse trace element signatures. There are now geographically-dispersed, widespread examples with Isua BIF-like REE + Y signatures, that are interpreted as chemically unaltered, albeit metamorphosed, chemical sediments. Other samples retain remnants of LREE depletion but are beginning to lose the distinct La, Eu and Y positive anomalies and are interpreted as metasomatised chemical sediments. Finally there are some siliceous samples with completely different trace element patterns that are interpreted as rocks of non-sedimentary origin, and include metasomatised mafic rocks. The positive La/La*_SN, Eu/Eu*_SN and Y_SN anomalies found in Isua BIFs and other Eoarchaean Greenland samples, such as G91/26 from Akilia, suggests that the processes of carbonate ion complexation controlling the REE − Y patterns were already established in the hydrosphere at the start of the sedimentary record 3,600–3,850 Ma ago. This is in accord with the presence of Eoarchaean siderite-bearing marbles of sedimentary origin, and suggests that CO₂ may have been a significant greenhouse gas at that time.     

Structural,textural, geochemical and isotopic signatures of synglaciogenic Neoproterozoic banded iron formations (BIFs) at Bafq mining district (BMD), Central Iran: The possible Ediacaran missing link of BIFs in Tethyan metallogeny

The Neoproterozoic magnetite–apatite–hematite–pyrolusite–jaspilite deposits in the Bafq mining district (BMD) contain more than 1.7 Gt ores with an average grade of 50 wt.% Fe and 0.01 to 7.78 wt.% P and were probably formed between 635 and 547 Ma in a riftogenic felsic submarine exhalative sequence of the Esfordi Formation. The ore zones occur in proximal zone of magnetite-rich albitized rhyolite (keratophyres), interdistal zone of rhyolitic tuff–tuffaceous sediments and distal zone of pyrolusite–jaspilite. These sequences are covered by the diamictites and cap carbonates. The BIFs are linked to the altered rhyolites–rhyodacites, jaspilites and diamictites and contain magnetite, hematite and apatite. The presence of Spriggina, Dickinsonia, Medusites and Persimedusites chahgazensis (Sennewald and Krüger, 1979; Hahn and, Pflug; McCall, 2006) in the Kushk shale member of the Esfordi Formation conforms to the Australian fauna of the Ediacaran period (635–540). This relative age is supported by some reliable Pb isotopic data (635–547 Ma) on galena, monazite and apatite (Huckriede et al., 1962; Torab, 2008; Stosch et al., 2011). The most frequent structures–textures in the ore zones include felsic autobrecciation, massive, colloidal, banded, detrital and glaciogenic. The BIFs are highlighted by high values of LREE fractionation and no significant Eu and Ce anomalies. The ores show high values of Fe₂O₃ (14–60%), and SiO₂ (4–34%), and low contents of Al (3.32%), Cr (21.48 ppm), Co (42.82 ppm), Ni (125 ppm), V (868 ppm), and Ti (0.13%) similar to those of the Ediacaran–Rapitan BIFs. The cap carbonates show depletion in δ¹³C, with a range from − 0.43 to − 6.6 per mil and then return to near excursion of about + 2.97‰ in the Lower Cambrian carbonates. These are followed by δ¹⁸O values, which range from − 6.64 to − 11.86‰. The presence of jaspilites, diamictites, C and O isotopic signatures, REE patterns, and immobile element relationships highlights a glaciogenic BIF. Importantly, the glaciogenic structures–textures and jaspilites do not support the misconception of the previously proposed magmatic–carbonatitic and metasomatic–hydrothermal IOCG–Kiruna ore deposits.     

Petrography and geochemistry of the Shilu Fe–Co–Cu ore district,South China: Implications for the origin of a Neoproterozoic BIF system

The Shilu Fe–Co–Cu ore district is situated in the western Hainan Province of south China. This district consists of the upper Fe-rich layers and the lower Co–Cu ores, which are mainly hosted within the Neoproterozoic Shilu Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Three facies of metamorphosed BIFs, the oxide, the silicate–oxide and the sulfide–carbonate–silicate, have been identified within the Shilu Group. The oxide banded iron formation (BIF) facies (quartz itabirites or Fe-rich ores) consists of alternating hematite-rich and quartz-rich microbands. The silicate–oxide BIF facies (amphibolitic itabirites or Fe-poor ores) comprises alternating millimeter to tens of meter scale, magnetite–hematite-rich bands with calc-silicate-rich macro- to microbands. The sulfide–carbonate–silicate BIF facies (Co–Cu ores) contain alternating cobaltiferous pyrite, cobaltiferous pyrrhotite and chalcopyrite macrobands to microbands mainly with dolomite–calcite, but also with minor sericite–quartz bands. Blasto-oolitic, pelletoidal, colloidal, psammitic, and cryptocrystalline to microcrystalline textures, and blasto-bedding structures, which likely represent primary sedimentation, are often observed in the Shilu BIF facies.The Shilu BIFs and interbedded host rocks are generally characterized by relatively low but variable ∑ REE concentrations, LREE depletion and/or MREE enrichment relative to HREE, and no Ce, Gd and Eu anomalies to strongly positive Ce, Gd and Eu anomalies in the upward-convex PAAS-normalized REY patterns, except for both the banded or impure dolostones with nil Ce anomaly to negative Ce anomalies and negative La anomalies, and the minor sulfide–carbonate–silicate BIF facies with moderately negative Eu anomalies. They also contain relatively low but variable HFSE abundances as Zr, Nb, Hf, Th and Ti, and relatively high but variable abundances of Cu, Co, Ni, Pb, As, Mn and Ba. The consistently negative ε_Nd(t) values range from − 4.8 to − 8.5, with a T_DM age of ca. 2.0 Ga. In line with the covariations between Al₂O₃ and TiO₂, Fe₂O₃ + FeO and SiO₂, Mn and Fe, Zr and Y/Ho and REE, and Sc and LREE, the geochemical and Sm–Nd isotopic features suggest that the precursors to the Shilu BIFs formed from a source dominated by seafloor-derived, high- to low temperature, acidic and reducing hydrothermal fluids but with variable input of detrital components in a seawater environment. Moreover, the involved detrital materials were sourced dominantly from an unknown, Paleoproterozoic or older crust, with lesser involvement from the Paleo- to Mesoproterozoic Baoban Group underlying the Shilu Group.The Shilu BIFs of various facies are interpreted to have formed in a shallow marine, restricted or sheltered basin near the rifted continental margin most likely associated with the break-up of Rodinia as the result of mantle superplume activity in South China. The seafloor-derived, periodically upwelling metalliferous hydrothermal plume/vent fluids under anoxic but sulfidic to anoxic but Fe^2 +-rich conditions were removed from the plume/vent and accumulated in the basin, and then variably mixed with terrigenous detrital components, which finally led to rhythmic deposition of the Shilu BIFs.     

Continentally-derived solutes in shallow Archean seawater: Rare earth element and Nd isotope evidence in iron formation from the 2.9 Ga Pongola Supergroup, South Africa

The chemical composition of surface water in the photic zone of the Precambrian ocean is almost exclusively known from studies of stromatolitic carbonates, while banded iron formations (IFs) have provided information on the composition of deeper waters. Here we discuss the trace element and Nd isotope geochemistry of very shallow-water IF from the Pongola Supergroup, South Africa, to gain a better understanding of solute sources to Mesoarchean shallow coastal seawater. The Pongola Supergroup formed on the stable margin of the Kaapvaal craton ∼2.9 Ga ago and contains banded iron formations (IFs) that represent the oldest documented Superior-type iron formations. The IFs are near-shore, pure chemical sediments, and shale-normalized rare earth and yttrium distributions (REY_SN) exhibit positive La_SN, Gd_SN, and Y_SN anomalies, which are typical features of marine waters throughout the Archean and Proterozoic. The marine origin of these samples is further supported by super-chondritic Y/Ho ratios (average Y/Ho = 42). Relative to older Isua IFs (3.7 Ga) from Greenland, and younger Kuruman IFs (2.5 Ga) also from South Africa, the Pongola IFs are depleted in heavy rare earth elements (HREE), and appear to record variations in solute fluxes related to sea level rise and fall. Sm-Nd isotopes were used to identify potential sediment and solute sources within pongola shales and IFs. The ?_Nd(t) for Pongola shales ranges from −2.7 to −4.2, and ?_Nd(t) values for the coeval iron-formation samples (range −1.9 to −4.3) are generally indistinguishable from those of the shales, although two IF samples display ?_Nd(t) as low as −8.1 and −10.9. The similarity in Nd isotope signatures between the shale and iron-formation suggests that mantle-derived REY were not a significant Nd source within the Pongola depositional environment, though the presence of positive Eu anomalies in the IF samples indicates that high-T hydrothermal input did contribute to their REY signature. Isotopic mass balance calculations indicate that most (?72%) of the Nd in these seawater precipitates was derived from continental sources. If previous models of Fe-Nd distributions in Archean IFs are applied, then the Pongola IFs suggest that continental fluxes of Fe to Archean seawater were significantly greater than are generally considered.     

The composition and genesis of the Mesoarchean Dagushan banded iron formation (BIF) in the Anshan area of the North China Craton

The Dagushan BIF-hosted iron deposit in the Anshan–Benxi area of the North China Craton (NCC) has two types of iron ore: quartz–magnetite BIF (Fe₂O₃^T < 57 wt.%) and high-grade iron ore (Fe₂O₃^T > 90 wt.%). Chlorite-quartz schist and amphogneiss border the iron orebodies and are locally present as interlayers with BIFs; chlorite-quartz schist and BIFs are enclosed by amphogneiss in some locations. The quartz–magnetite BIFs are enriched in HREEs (heavy rare earth elements) with positive La, Eu and Y anomalies, indicating their precipitation from marine seawater with a high-temperature hydrothermal component. Moreover, these BIFs have low concentrations of Al₂O₃, TiO₂ and HFSEs (high field strength elements, e.g., Zr, Hf and Ta), suggesting that terrigenous detrital materials contributed insignificantly to the chemical precipitation. The high-grade iron ores exhibit similar geochemical signatures to the quartz–magnetite BIFs (e.g., REE patterns and Y/Ho ratios), implying that they have identical sources of iron. However, these ores have different REE (rare earth element) contents and Eu/Eu* values, and the magnetites contained within them exhibit diverse REE contents and trace element concentrations, indicating that the ores underwent differing formation conditions, and the high-grade ores are most likely the reformed product of the original BIFs.The chlorite-quartz schist and amphogneiss are characterized by high SiO₂ and Al₂O₃ contents and exhibit variable abundances of REEs, enrichment in LREEs (light rare earth elements), negative anomalies in HFSEs (e.g., Nb, Ta, P and Ti) and positive anomalies in LILEs (large ion lithophile elements, e.g., Rb, Ba, U and K). A protolith reconstruction indicates that the protoliths of the chlorite-quartz schist are felsic volcanic rocks. SIMS and LA-ICP-MS zircon U–Pb dating indicate that this schist formed at approximately 3110 to 3101 Ma, which could represent the maximum deposition age of the Dagushan BIF. However, two groups of zircons from the amphogneiss are identified: 3104 to 3089 Ma zircons that are most likely derived from the chlorite-quartz schist and 2997 to 2995 Ma zircons, which are interpreted to represent the time of protolith crystallization. Thus, the Dagushan BIF most likely formed before 2997 to 2995 Ma. The ~ 3.1 Ga zircons yield ε_Hf(t) values of − 8.07 to 5.46, whereas the ~ 3.0 Ga zircons yield ε_Hf(t) values of − 3.96 to 2.09. These geochemical features suggest that the primitive magmas were derived from the depleted mantle with significant contributions of ancient crust.     

Changes of oceanic environment before and after the Paleoproterozoic Great Oxidation Event(GOE): Evidence from petrography and geochemistry of banded iron formation(BIF)from the North China Craton

Banded iron formation(BIF)belongs to sedimentary rocks formed in Precambrian marine,which can directly reflect the redox state of the ancient oceans. Mineral composition and geochemistry of BIF can reveal the relative changes of oxygen contents of ancient atmosphere-ocean. The Neoarchean and Paleoproterozoic BIFs widely distributed in the North China Craton(NCC),are the ideal research objects for understanding the changes of the ancient ocean redox environment before and after the Paleoproterozoic Great Oxidation Event(GOE). Our previous studies indicated that the sedimentary facies of the Neoarchean BIF in the NCC are mainly magnetite-type oxide and silicate,with minor carbonate. The sedimentary facies of the Paleoproterozoic BIF are hematite- and magnetite-type oxide,silicate and carbonate,of which the hematite-oxide facies is unique to the Paleoproterozoic BIF. The above mineralogical features suggest that the redox conditions of the Neoarchean and Paleoproterozoic seawater are different. The rare earth element composition of the Neoarchean BIF in the NCC lacks a strong negative Ce anomaly,reflecting that the oxygen content of contemporary seawater is very low and the marine is anoxic. However,a small amount of BIFs in the NCC also present the negative Ce anomalies and a wide range of Th/U ratios,indicating that the local water of the Neoarchean ocean had relatively high oxygen content and was at a weak oxidation state. Compared with the Neoarchean BIFs,the Paleoproterozoic BIFs present a wide range of Ce anomalies(i.e.,no Ce anomalies,positive Ce anomalies and negative Ce anomalies). The hematite-bearing BIF has an obvious negative Ce anomalies,implying that the oxygen content and redox state of Paleoproterozoic seawater changed significantly. Combined with the ratios of Ni/Co,V/(V+Ni)and Th/U of the BIFs in the NCC,the Paleoproterozoic oceans exhibited a suboxidation to oxidation environment. Besides,Neoarchean BIF is strongly enriched in heavy iron isotopes and the non-mass fractionation of S isotope is obvious,whereas the Paleoproterozoic BIF is relatively enriched in light iron isotopes and the non-mass fractionation of S isotope is not obvious. It is summarized that the Neoarchean marine is anoxic,but the oxygen‘oasis' may exist locally,implying that photosynthetic oxygen production already existed in the Late Neoarchean. The ancient ocean presented a layered characteristics during and after the GOE,indicating that the shallow water was generally oxidized and the deep water was reduced.     

辽宁本溪歪头山条带状铁矿的成因类型、形成时代及构造背景

辽宁鞍本地区位于华北克拉通东北缘,分布有诸多大型-特大型条带状铁矿床。本文对该区歪头山铁矿进行了岩石学、矿物学及年代学研究。歪头山铁建造以条带状铁矿石为主,兼含有少量的块状矿石,其顶底板围岩及矿体夹层主要为太古界鞍山群斜长角闪岩。元素地球化学分析表明,铁矿石富集重稀土[(La/Yb)_PAAS=0.24~0.33],具La正异常(La/La^*=1.43~1.61)、Eu正异常(Eu/Eu^*=2.40~4.54)及Y正异常(Y/Y^*=1.10~1.30),Y/Ho值平均30.59,Sr/Ba值平均17.62,Ti/V值平均19.45,反映成矿物质可能来源于由海底火山活动带来的高温热液与海水的混合溶液。铁矿石无明显Ce负异常(Ce/Ce^*=0.92~1.06),暗示BIF沉积时海水处于缺氧环境。除Fe₂O₃^T与SiO₂外,铁矿石中其它氧化物含量均非常低,且贫Th、U、Zr等具有陆源性质的元素,表明大陆碎屑物质对BIF贡献极少。斜长角闪岩稀土元素配分型式近于平坦[(La/Yb)_N=0.80~1.10],无明显Ce异常(Ce/Ce^*=0.95~0.99)与Eu异常(Eu/Eu^*=0.88~1.16);其大离子亲石元素富集,高场强元素无明显亏损。地球化学分析表明,斜长角闪岩原岩可能为产于弧后盆地的玄武质火山岩。锆石形态与微量元素分析显示,斜长角闪岩中的锆石均属岩浆成因。SIMS锆石U-Pb定年显示斜长角闪岩原岩形成于2533±11Ma,代表了歪头山BIF的成矿年龄;在玄武质岩浆喷发过程中,还捕获了一组年龄为2610±5Ma的锆石。电子探针分析显示磁铁矿成分纯净(FeO^T=92.04%~93.05%),其标型组分特征暗示歪头山BIF属沉积变质型铁矿。综合分析认为,歪头山铁矿属Algoma型BIF,成矿与弧后盆地岩浆活动密切相关,指示了新太古代末华北克拉通普遍发育的一期BIF成矿事件。     

Petrology and geochemistry of the banded iron-formations from Ntem complex greenstones belt,Elom area,Southern Cameroon: Implications for the origin and depositional environment

Banded iron-formations (BIFs) form an important part of the Archaean to Proterozoic greenstone belts in the Southern Cameroon. In this study, major, trace and REE chemistry of the banded iron-formation are utilized to explore the source of metals and to constraint the origin and depositional environment of these BIFs. The studied BIF belongs to the oxide facies iron formations composed mainly of iron oxide (mainly magnetite) mesobands alternating with quartz mesobands. The mineralogy of the BIF sample consists of magnetite and quartz with lesser amount of secondary martite, goethite and trace of gibbsite and smectite. The major element chemistry of these iron-formations is remarkably simple with the main constituents being SiO₂ and Fe₂O₃ which constitute 95.6–99.5% of the bulk rock. Low Al₂O₃, TiO₂, and HFSE concentrations show that they are relatively detritus-free chemical sediments. The Pearson’s correlation matrix of major element reveals that there is a strong positive correlation (r = 0.99) of Al with Ti and no to weak negative correlation of Ti with Mn, Ca and weak positive correlation of Si with Ca, suggesting the null to very minor contribution of detrital material to chemical sediment. The trace elements with minor enrichments are transition metals such as Zn, Cr, Sr, V and Pb. This is an indicator of direct volcanogenic hydrothermal input in chemical precipitates. The studied BIF have a low ΣREE content, ranging between 0.41 and 3.22 ppm with an average of 0.87 ppm, similar to that of pure chemical sediments. The shale-normalized patterns show depletion in light REE, slightly enrichment in heavy REE and exhibit weak positive europium anomalies. These geochemical characteristics indicate that the source of Fe and Si was the result of deep ocean hydrothermal activity admixed with sea water. The absence of a large positive Eu anomaly in the studied BIF indicates an important role of low-temperature hydrothermal solutions. The chondrite-normalized REE patterns are characterized by LREE-enriched (Mean La_CN/Yb_CN = 8.01) and HREE depletion (Mean Tb_CN/Yb_CN = 1.61) patterns and show positive Ce anomalies. With the exception of one sample (LBR133), all of the BIF samples analyzed during this study have positive Ce anomalies on both chondrite- and PASS-normalized plots. This may indicate that the BIFs within the Elom area were formed within a redox stratified ocean. The positive Ce anomalies in the studied samples likely suggest that the basin in which Fe formations were deposited was reducing with respect to Ce, probably in the suboxic or anoxic seawaters.     

A mixed seawater and hydrothermal origin of superior-type banded iron formation (BIF)-hosted Kouambo iron deposit,Palaeoproterozoic Nyong series,Southwestern Cameroon: Constraints from petrography and geochemistry

The Kouambo iron deposit contains banded iron formations (BIFs) and is located in the northwestern margin of the Congo craton. The BIFs are hosted in Palaeoproterozoic Nyong series, a dominantly metasedimentary formations, which were metamorphosed into greenschist to granulite facies. The Kouambo BIFs are medium- to coarse-grained banded rocks consisting of alternation of Si-rich and Fe-rich mesobands, and belong to oxide facies iron formations. Geochemistry analyses reveal that these iron formations are composed of > 96 wt% Fe₂O₃ and SiO₂ and have low concentrations of Al₂O₃, TiO₂ and trace HFSE, suggesting chemical precipitates of silica and iron. Moreover, these BIFs have low concentrations of Al₂O₃, TiO₂ and trace HFSEs (high field strength elements, e.g., Zr, Hf, Ta, Pb and Th), suggesting that terrigenous detrital materials contributed insignificantly to the sedimentation. The Post-Archean Australian Shale (PAAS)-normalized REE-Y patterns display seawater-like profile: minor LREE depletion and HREE enrichment, positive Y anomalies. However, they display positive Eu and negative Ce anomalies, and low Y/Ho ratio (average 29), which suggest the influence of the hydrothermal fluids. The weak positive Eu/Eu*(_PAAS) ratio (average 1.5), associated with the low V (17.5 ppm), Co (6.1 ppm) and Ni (27.5 ppm) contents similar to other Superior-type BIFs worldwide, are consistent with the deposition of the Kouambo BIFs in continental marginal sea or back-arc basin environment. In summary, the Kouambo BIFs show a seawater-like REE + Y signature, however, the positive Eu anomalies and reduced Y/Ho ratios relative to seawater indicates a possible mixing with hydrothermal fluids (∼ 0.5%).     

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.     

Extreme positive Ce-anomalies in a 3.0 Ga submarine volcanic sequence,Murchison Province: Oxygenated marine bottom waters

Systematic positive anomalies of Ce, where Ce/Ce* spans 2.1 to 11.4, are present in basalts and rhyolites of a 2.96 Ga submarine volcanic sequence of the Murchison Province, Western Australia. This volcanic sequence is host to a stratabound Cu–Zn deposit that formed on the seafloor from a seawater hydrothermal system. These are true Ce anomalies as Pr/Pr* < 1. In modern oxygenated marine water Ce is sequestered by Mn-oxides and hydroxides, which coprecipitate with Fe-oxides and hydroxides as nodules and crusts on the ocean floor, as well as Fe–Mn chemical sediments from hydrothermal systems at ocean spreading centers. Fe–Mn sediments have positive Ce anomalies and marine water complementary negative anomalies. Such Ce anomalies have not formerly been reported for Archean hydrothermally altered volcanic rocks. These extreme anomalies are attributed to Mn-transport in shallow-circulating oxygenated marine bottom waters peripheral to the deeper, hotter, hydrothermal system from which the Cu–Zn deposit formed, and record an oxygenated marine environment ~ 500 Ma before the so-called great oxidation event at ~ 2.4 Ga. Results for positive Ce anomalies in the Golden Grove volcanic sequence are complementary to negative anomalies in Archean BIF, collectively stemming from particulate scavenging of Ce^+ 3 in an oxic water column.     

Petrography and geochemistry of the Mesoarchean Bikoula banded iron formation in the Ntem complex (Congo craton), Southern Cameroon: Implications for its origin

Precambrian banded iron formations (BIFs) represent an important source of mineable iron, as well as an archive recording secular changes in the chemistry of the Earth’s early oceans. Here we report petrographic and geochemical characteristics of unweathered drill core samples from the Bikoula BIF, a virtually uncharacterized oxide facies iron formation, hosted in the Mesoarchean Ntem complex, southern Cameroon. The BIF is cross-cut with syenitic veins. The entire succession is highly deformed and metamorphosed under granulite facies conditions. The BIF is characterized by alternating micro-bands of magnetite, quartz and pyroxene. Sulfides (pyrite, pyrrhotite, and chalcopyrite), oligoclase, ferro-pargasite, biotite and ilmenite occur as minor phases. The presence of pyroxene, ferro-pargasite and oligoclase, relatively high contents of major elements such as Al₂O₃ (0.76–7.52 wt.%), CaO (1.95–4.90 wt.%), MgO (3.78–5.59 wt.%), as well as positive correlations among Al₂O₃, TiO₂, HFSEs, LILEs and transition metals (V, Cr, Ni, Cu and Zn), suggest that the BIF protolith included a significant amount of clastic material. Several samples have preserved seawater-like PAAS-normalized REE-Y patterns, including LREE depletion, and positive La and Y anomalies. Positive Eu anomalies observed in some of the analyzed samples indicate influx of hydrothermal fluids (possibly including Fe and Si) within the basin where the BIF precipitated. However, few samples show unusual negative Eu anomalies that likely result from a large proportion of clastic contamination. The lack of Ce anomalies suggests that the Bikoula BIF was deposited in a basin that was (at least partly) anoxic or suboxic, where it was possible to transport and concentrate dissolved Fe²⁺.     

Precambrian banded iron formations in the North China Craton: Silicon and oxygen isotopes and genetic implications

Banded iron formations (BIFs) are Precambrian chemical marine sedimentary formations that record major transitions of chemical composition, and oxidation–reduction state of oceans at the time of their deposition. In this paper, we report silicon and oxygen isotope compositions of a variety of BIFs from the North China Craton (NCC) in order to deduce the mechanism of their formation. Quartz in the various types of BIFs from the NCC are generally depleted in ³⁰Si, where δ³⁰Si_NBS-28 values range from − 2.0‰ to − 0.3‰ (average, − 0.8‰), similar to δ³⁰Si_NBS-28 values measured from modern submarine black chimneys and sinters. The δ¹⁸O_V-SMOW values of quartz in the BIFs are relatively high (8.1‰–21.5‰; average, 13.1‰), similar to those of siliceous rock formed by hydrothermal activities. The δ³⁰Si_NBS-28 values of quartz in magnetite bands are commonly lower than those of quartz in adjacent siliceous bands within the same sample, whereas δ¹⁸O_V-SMOW values are higher in the magnetite bands. A negative correlation is observed between δ³⁰Si_NBS-28 and δ¹⁸O_V-SMOW values of quartz from siliceous and magnetite bands in BIF from Fuping, Hebei Province. The isotopic compositions of silicon and oxygen of quartz in BIFs provide insights for the formation mechanisms of silicon–iron cyclothems in BIFs. After the silicon- and iron-rich hydrothermal solution was injected onto the seabed, the abrupt temperature drop caused oversaturation of silicic acid, resulting in rapid precipitation of SiO₂ and deposition of siliceous layers. Ferric hydroxide was precipitated later than SiO₂ because of low free-oxygen concentration in the ocean bottom. Progressive mixing of hydrothermal solution with seawater caused a continuous drop in temperature and an increase in Eh values, resulting in gradual oxidation of hydrothermal Fe^2 + and deposition of iron-rich layers. In summary, each silicon–iron cyclothem marks a large-scale submarine hydrothermal exhalation. The periodic nature of these exhalations resulted in the formation of regular silicon–iron cyclothems. The widespread distribution of BIFs indicates that volcanism and submarine hydrothermal exhalation were extensive; the low δ³⁰Si_NBS-28 and high δ¹⁸O _V-SMOW values of the BIFs indicate that the temperature of seawater was relatively high at the time of BIF formation, and that concentrations of Fe^2 + and H₄SiO₄ in seawater were saturated.     

Biogenic and abiogenic low-Mg calcite (bLMC and aLMC): Evaluation of seawater-REE composition,water masses and carbonate diagenesis

The ΣREE and shale-normalized (PAAS) REE_SN values of modern brachiopods (biogenic low-Mg calcite: bLMC) represented by several species from high- to low latitudes, from shallow- to deep waters and from warm- and cold-water environments, define three distinct average ‘seawater’ trends. The warm- and cold-water brachiopods define two indistinguishable (p < 0.050) groups that mimic open-ocean seawater REE chemistry, exhibiting the typical LREE enrichment with a slightly positive to negative Ce anomaly followed by an otherwise invariant series. Other recent brachiopods from an essentially siliciclastic seabed environment are distinct in both ΣREE and REE_SN trends from the previous two populations, showing a slight enrichment in the MREEs and an increasing trend in the HREEs. Other groups of modern brachiopods are characterized by elevated REE_SN trends relative to the ‘normal’ groups as well as by complexity of the series trends. The most characteristic feature is the decrease in the HREEs in these brachiopods from areas of unusual productivity (i.e., such as upwelling currents, fluvial input and aerosol dust deposition). Preserved brachiopods from the Eocene and Silurian exhibit REE_SN trends and Ce anomalies similar to that of the ‘open-ocean’ modern brachiopods, although, their enriched ΣREE concentrations suggest precipitation of bLMC influenced by extrinsic environmental conditions.Preservation of the bLMC was tested by comparing the ΣREE and REE_SN trends of preserved Eocene brachiopods to those of Oligocene brachiopods that were altered in an open diagenetic system in the presence of phreatic meteoric-water. The altered bLMC is enriched by approximately one order of magnitude in both ΣREE and REE_SN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REE_SN of preserved Silurian brachiopod bLMC were compared to those of their enclosing altered lime mudstone, which exhibits features of partly closed system, phreatic meteoric-water diagenesis. Despite these differences in the diagenetic alteration systems and processes, the ΣREEs and REE_SN trends of the bLMC of altered brachiopods and of originally mixed mineralogy lime mudstones (now diagenetic low-Mg calcite) are enriched by about one order of magnitude relative to those observed in the coeval and preserved bLMC.In contrast to the changes in ΣREE and REE_SN of carbonates exposed to phreatic meteoric-water diagenesis, are the REE compositions of late burial calcite cements precipitated in diagenetically open systems from burial fluids. The ΣREE and REE_SN trends of the burial cements mimic those of their host lime mudstone, with all showing slight LREE enrichment and slight HREE depletion, exhibiting a ‘chevron’ pattern of the REE_SN trends. The overall enrichment or depletion of the cement REE_SN trends relative to that of their respective host rock material reflects not only the openness of the diagenetic system, but also strong differences in the elemental and REE compositions of the burial fluids. Evaluation of the (Ce/Ce*)_SN and La = (Pr/Pr*)_SN anomalies suggests precipitation of the burial calcite cements essentially in equilibrium with their source fluids.