Ferropericlase—a lower mantle phase in the upper mantle

Experiments on compositions along the join MgO–NaA³⁺Si₂O₆ (A=Al, Cr, Fe³⁺) show that sodium can be incorporated into ferropericlase at upper mantle pressures in amounts commonly found in natural diamond inclusions. These results, combined with the observed mineral parageneses of several diamond inclusion suites, establish firmly that ferropericlase exists in the upper mantle in regions with low silica activity. Such regions may be carbonated dunite or stalled and degassed carbonatitic melts. Ferropericlase as an inclusion in diamond on its own is not indicative of a lower mantle origin or of a deep mantle plume. Coexisting phases have to be taken into consideration to decide on the depth of origin. The composition of olivine will indicate an origin from the upper mantle or border of the transition zone to the lower mantle and whether it coexisted with ferropericlase in the upper mantle or as ringwoodite. The narrow and flat three phase loop at the border transition zone—lower mantle together with hybrid peridotite plus eclogite/sediments provides an explanation for the varying and Fe-rich nature of the diamond inclusion suite from Sao Luiz, Brazil.     

On the implications of the coupled evolution of the deep planetary interior and the presence of surface ocean water in hydrous mantle convection

We investigate the influence of the deep mantle water cycle incorporating dehydration reactions with subduction fluxes and degassing events on the thermal evolution of the Earth as a consequence of core–mantle thermal coupling. Since, in our numerical modeling, the mantle can have ocean masses ∼12 times larger than the present-day surface ocean, it seems that more than 13 ocean masses of water are at the maximum required within the planetary system overall to partition one ocean mass at the surface of the present-day Earth. This is caused by effects of water-dependent viscosity, which works at cooling down the mantle temperature significantly so that the water can be absorbed into the mantle transition zone and the uppermost lower mantle. This is a result similar to that without the effects of the thermal evolution of the Earth's core (Nakagawa et al., 2018). For the core's evolution, it seems to be expected for a partially molten state in the deep mantle over 2 billion years. Hence, the metal–silicate partitioning of hydrogen might have occurred at least 2 billion years ago. This suggests that the hydrogen generated from the phase transformation of hydrous-silicate-hosted water may have contributed to the partitioning of hydrogen into the metallic core, but it is still quite uncertain because the partitioning mechanism of hydrogen in metal–silicate partitioning is still controversial. In spite of many uncertainties for water circulation in the deep mantle, through this modeling investigation, it is possible to integrate the co-evolution of the deep planetary interior within that of the surface environment.     

Dissociation of CAS phase in the uppermost lower mantle

The high-pressure stability limit of calcium aluminosilicate (CAS) phase has been examined in its end-member CaAl₄Si₂O₁₁ composition at 18–39 GPa and 1,670–2,300 K in a laser-heated diamond-anvil cell (LHDAC). The in-situ synchrotron X-ray diffraction measurements revealed that the CAS phase decomposes into three-phase assemblage of cubic Al-bearing CaSiO₃ perovskite, Al₂O₃ corundum, and SiO₂ stishovite above 30 GPa and 2,000 K with a positive pressure–temperature slope. Present results have important implications for the subsolidus mineral assemblage of subducted sediment and the melting phase relation of basalt in the lower mantle.     

下地幔矿物研究及其进展

文中综述了20世纪90年代以来对下地幔矿物高温高压研究的进展,详细评论了下地幔温压下(Mg,Fe)SiO3钙钛矿的稳定性、(Mg, Fe)SiO3 钙钛矿和(Mg, Fe)O镁方铁矿的高压状态方程和热弹性及高压熔化、核幔边界温压下铁和硅酸盐的化学反应等几个热点问题;探讨了下地幔的矿物学组成,对下地幔的地震波速异常给出了可能的矿物学解释;介绍了国内同领域的研究工作;展望了下地幔矿物研究的发展方向。     

3D structure of the Earth's lower mantle

We present an overview of the present knowledge of the Earth's lower mantle 3D structure, as currently obtained owing to progress, in the last ten years, in seismic tomography as well as forward modelling of seismic travel times and waveforms. We discuss constraints that seismic modelling brings to the debate concerning major geodynamical questions, in particular the issue of global ‘1 layer’ or ‘2 layer’ circulation, of the missing geochemical reservoir, as well as of the role in global dynamics of the thermochemical boundary layer at the base of the mantle.     

Dependence on pressure of conduction by hopping of small polarons in minerals of the Earth's lower mantle

Electrical conductivity of the lower mantle-like assemblage (Mg,Fe)SiO₃ perovskite-(Mg,Fe)O magnesiowüstite is usually analyzed using the quasi-chemical Arrhenian approach of diffusion. The conductivity of this assemblage has often been attributed to hopping of small polarons, because of the low value of the activation energy and the small negative activation volume. However, the solid-state physics approach can provide more arguments, for or against conduction by polarons. We have tried to bridge the gap between the two approaches and identify the physical quantities entering the phenomenological activation parameters. In particular, we have investigated the pressure dependence of the activation energy, and the physical meaning of the activation volume. Hopping is controlled by the binding energy of the polaron and by the value of the exchange integral, which increases with pressure causing the observed decrease of the activation energy. From the physical theory and the results of experiments at pressures up to 40 GPa and temperatures up to 400 ^∘C, we have estimated the values of parameters characteristic of polarons: radius, mobility, time between jumps and adiabaticity. These values are compatible with conduction by small adiabatic polarons. The consequences for extrapolations to lower mantle conditions of the presence of a temperature dependent preexponential term in the expression for conductivity have been examined. It was found that the extrapolations are not significantly different from those using the Arrhenius equation. Received: 5 November 1998 / Revised, accepted: 4 May 1999     

中国东部及西秦岭地区新生代岩石圈地幔中的相转变带及其温压条件

五相（橄榄石＋斜方辉石＋单斜辉石＋石榴石＋尖晶石）共存的地幔橄榄岩捕虏体是来自岩石圈地幔相转变带的直接样品.中国东部及西秦岭地区晚第三至第四纪碱性火山岩携带的少量五相共存的地幔橄榄岩捕虏体为探讨这些地区新生代岩石圈地幔中相转变带提供了宝贵的样品.本文根据地幔橄榄岩捕虏体中石榴石和尖晶石的产出状况,将这些橄榄岩捕虏体分为三类：第一类橄榄岩中尖晶石为粒状残核,尖晶石外缘被石榴石的反应边包围.这种橄榄岩捕虏体代表尖晶石-石榴石相转变带的上限,故称为尖晶石带橄榄岩;第二类橄榄岩中尖晶石和石榴石以单颗粒零散分布为特征,二者共存但未见明显的相转变关系.这类橄榄岩多位于相转变带中部,拟称为尖晶石-石榴石过渡带橄榄岩;第三类橄榄岩中以石榴石为主,尖晶石和辉石等微晶构成石榴石反应边.这类橄榄岩代表尖晶石-石榴石相转变带的下限,故称为石榴石带橄榄岩.因此,根据不同类型橄榄岩捕虏体中矿物的组成,结合温度压力估算即可确定岩石圈地幔中相转变带的深度和厚度.本文通过对中国东部及西秦岭地区晚第三至第四纪碱性火山岩携带的尖晶石-石榴石二辉橄榄岩捕虏体的温度压力估算来进一步厘定中国东部新生代岩石圈地幔中的相转变带深度和厚度.     

Laurite and zircon from the Finero chromitites (Italy): New insights into evolution of the subcontinental mantle

Chromitites enclosed within metasomatised Finero phlogopite peridotite (FPP) contain accessory platinum-group minerals, base metal (BM) sulfides, baddeleyite, zircon, zirconolite, uraninite and thorianite. To provide new insights into mantle-crustal interaction in the Finero lithosphere this study evaluates (1) the mineral chemistry and Os-isotope composition of laurite, (2) the crystal morphology, internal structure, in-situ U-Pb, trace-element and Hf-isotope data of zircon from two chromitite localities at Alpe Polunia and Rio Creves. The osmium isotope results reveal a resticted range of ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for laurite at Alpe Polunia (0.1247–0.1251, mean 0.1249 ± 0.0001). Re-Os model ages (T_RD) of laurite reflect an Early Paleozoic partial melting event (ca 450 Ma or older), presumably before the Variscan orogeny. The Os isotopic composition of laurite/chromitite probably preserves their mantle signature and was not affected by later metasomatic processes. U-Pb and Hf-isotope data show that the Finero chromitites have distinct zircon populations with peculiar morphology, internal cathodoluminescence textures, trace-element composition and an overall U-Pb age span from ∼310 Ma to 190 Ma. Three age peaks at Rio Creves (220 ± 4 Ma, 234.2 ± 4.5 Ma and 277.5 ± 3.2 Ma) are consistent with a prolonged formation and multistage zircon growth, in contrast to the common assumption of a single metasomatic event during chromitite formation. The trace-element signatures of zircons are comparable with those of mantle-derived zircons from alkaline ultramafic rocks, supporting the carbonatitic nature of the metasomatism. Hf-isotope compositions of the Finero zircons, with εHf values ranging mainly from −3 to +1, are consistent with crustal input during metasomatism and could indicate that the parental melts/fluids were derived from a relatively old source; the minimum estimates for Hf model ages are 0.8–1.0 Ga. Our findings imply that mantle rocks and metasomatic events at Finero have a far more complex geological history than is commonly assumed.     

河南省安林矽卡岩型铁矿的成岩时代和成矿物质来源探讨

位于华北克拉通中部的河南省安林铁矿是典型的邯邢式矽卡岩型铁矿,矿体产于闪长质岩石和中奥陶统灰岩的接触带。LA-ICPMS锆石U-Pb定年结果表明安林闪长岩体的侵位年龄为123.38±0.81Ma,略晚于华北克拉通东部地区的含矿岩体,形成于岩石圈大规模减薄伸展时期。但其中含有古老的锆石说明岩浆经历了地壳的混染。闪长质岩石具有相对低SiO2、高Mg#、高碱,富集Ba、Sr和LREE大离子亲石元素,亏损Nb、Ti、Ta等高场强元素的特点,暗示了其形成于岩石圈地幔。岩相学特征以及Harker图解指示了岩浆经历了较强的分离结晶作用,因此推断安林闪长岩可能是软流圈地幔上涌导致富集的岩石圈地幔发生部分熔融形成原始的辉长质岩浆在上升过程中或岩浆房中发生了以铁镁矿物为主的分离结晶作用,同时受到地壳物质的混染的结果。安林地区矿石具有和闪长岩体相似的稀土元素地球化学特征,反映铁的成矿作用与岩浆作用密切相关。矿床中闪长岩体、矽卡岩、矿石和碳酸盐围岩的主量元素对比研究表明钠交代作用引起Na、K、Fe、Si等元素在各岩类间的迁移,其中迁移出的铁为成矿提供了物质基础。安林地区初始岩浆富含水,分离结晶作用使残留岩浆水饱和而发生出溶;且岩浆在演化过程中受到区内膏盐层和碳酸盐地层的混染,促进了岩浆中流体的出溶并使出溶的流体富含Cl-,为有利于铁质活化的富Cl-岩浆流体的形成创造了条件。     

Petrogenetic link between amphibolites and the banded iron formation of the Yishui region in the North China Craton: implications for Neoarchean plume tectonics

ABSTRACT

Amphibolites have a genetically close relationship with banded iron formations (BIFs) in the North China Craton (NCC). The Yishui amphibolites in the NCC occur interbedded with Algoma–type Yishui BIFs as related wall rocks. A reconstruction of the amphibolite protolith was conducted based on the results of petrologic, mineralogic, and geochemical analyses. The Yishui amphibolites consist of actinolite, ferrohornblende, albite, orthoclase, biotite, quartz, magnetite with minor pyrite, titanite, and ilmenite. Their chemical compositions are mainly SiO₂, Fe₂O₃^T, CaO, and Al₂O₃ with subordinate TiO₂, MgO, Na₂O, K₂O, P₂O₅, and MnO. The chondrite–normalized rare earth element diagram, characterized by enriched light rare earth elements (La/Yb_CN = 19.51–24.05) with insignificant Eu and Ce anomalies, shows coherent trends. The primitive mantle–normalized multi–element spider diagram is enriched in large ion lithophile elements, high field strength elements, and light rare earth elements which are related to a mantle source. The results of this study, combined with previous literature data, indicate that the Yishui amphibolite protoliths had intraplate alkaline basalt affinities and were derived from an ocean island basalt–type mantle source with no contamination. The results also suggest that the basalts were primarily the product of small amounts of partial melting. Based on the results, it is considered that a mantle plume model is the most appropriate tectonic model as it better explains the amphibolite geochemical signature. Furthermore, this model can provide crucial information regarding the Archaean NCC tectonic evolution and can demonstrate the temporal and spatial relationships between the BIFs and wall rocks.     

Laboratory measurement of P-wave velocity in crustal and upper mantle xenoliths from Ichino-megata, NE Japan: ultrabasic hydrous lower crust beneath the NE Honshu arc

Ultrasonic laboratory measurements of P-wave velocity (Vp) were carried out up to 1.0 GPa in a temperature range of 25–400 °C for crustal and mantle xenoliths of Ichino-megata, northeast Japan. The rocks used in the present study cover a nearly entire range of lithological variation of the Ichino-megata xenoliths and are considered as representative rock samples of the lower crust and upper mantle of the back arc side of the northeast (NE) Honshu arc. The Vp values measured at 25 °C and 1.0 GPa are 6.7–7.2 km/s for the hornblende gabbros (38.6–46.9 wt.% SiO₂), 7.2 km/s for the hornblende-pyroxene gabbro (43.8 wt.% SiO₂), 6.9–7.3 km/s for the amphibolites (36.1–44.3 wt.% SiO₂), 8.0–8.1 km/s for the spinel lherzolites (46.2–47.2 wt.% SiO₂) and 6.30 km/s for the biotite granite (72.1 wt.% SiO₂). Combining the present data with the Vp profile of the NE Honshu arc [Iwasaki, T., Kato, W., Moriya, T., Hasemi, A., Umino, N., Okada, T., Miyashita, K., Mizogami, T., Takeda, T., Sekine, S., Matsushima, T., Tashiro, K., Miyamachi, H. 2001. Extensional structure in northern Honshu Arc as inferred from seismic refraction/wide-angle reflection profiling. Geophys. Res. Lett. 28 (12), 2329–2332], we infer that the 15 km thick lower crust of the NE Honshu arc is composed of amphibolite and/or hornblende (±pyroxene) gabbro with ultrabasic composition. The present study suggests that the Vp range of the lower crustal layer (6.6–7.0 km/s) in the NE Honshu arc, which is significantly lower than that obtained from various seismic measurements (e.g. the northern Izu-Bonin-Mariana arc: 7.1–7.3 km/s), is due to the thick hydrous lower crustal layer where hornblende, plagioclase and magnetite are dominant.     

赣中新余式铁矿地面和井中磁测资料综合处理解释

江西赣中铁矿位于江西省新余市,属沉积变质型铁矿,围岩均不具有磁性,具备磁法勘探找矿的物性基础。赣中铁矿矿体具有薄且深的特点,以往对矿区磁法勘探的资料解释工作未取得较好效果,勘探工作多以地质勘查和钻探为主。在充分了解研究区工作现状的基础上,利用小波分析方法对杨家桥矿区磁异常进行了多尺度分解,提取了深部场并加以解释;将重磁异常边界识别技术应用到磁测资料的解释中,划分了深部找矿远景区;最后,应用井中三分量磁测资料解释技术对松山工区62勘探线进行了精细反演解释,提供了定量解释结果,指出井中三分量磁测是寻找深部矿的有效方法,为赣中铁矿深部及外围找矿提供了新的工作思路。     

Mössbauer spectroscopy studies of the valence state of iron in chromite from the Luobusa massif of Tibet: implications for a highly reduced deep mantle

Mössbauer spectroscopy was applied to study the valence state of iron in chromite from massive, nodular and disseminated podiform chromitite ores of the Luobasa ophiolite massif of Tibet. The results show that Fe³⁺/ΣFe = 0.42 in chromite from massive ore, and Fe³⁺/ΣFe = 0.22 in chromite from nodular and disseminated ores. The massive ore records traces of ultra high pressure mineralogical assemblages, such as diamond inclusions in OsIr alloys, exsolution lamellae of coesite and diopside in chromite, inclusions of metal‐nitrides, native iron and others, which suggests a strongly reducing environment. In contrast, chromite from nodular and disseminated ore contains abundant low‐pressure OH‐bearing mineral inclusions whose formation requires a more oxidizing environment. The high value of Fe³⁺/ΣFe in the ‘reduced’ massive ore is explained by crystallographic stabilization of Fe³⁺ in a high‐pressure polymorph of chromite deep in the upper mantle despite low ambient fO₂ conditions. The presence of high‐pressure phases within the massive chromitite ore requires that the latter, together with its host peridotite, was transported in the solid state from a highly reduced deep mantle environment to shallow depths beneath an ocean spreading centre. It is suggested that in the low‐pressure environment of the spreading centre, the deep‐seated, reduced, massive chromitites partially reacted with their host peridotite in the presence of hydrous melt, yielding the nodular and disseminated chromitite ores. The preponderance of evidence suggests that the latter interaction involved boninitic melts in a supra‐subduction zone environment as proposed previously.     

A speculation on the structure of the D″ layer: The growth of anti-crust at the core–mantle boundary through the subduction history of the Earth

The growth curve of the continental crust shows that large amounts of continental crust formed in the early part of the Earth history are missing. In order to test a hypothesis that the former crust was subducted to the deep mantle, we performed phase assemblage analysis in the systems of mid-oceanic ridge basalt (MORB), anorthosite, and tonalite–trondhjemite–granite (TTG) down to the core–mantle boundary (CMB) conditions. Results show that all these materials can be subducted to the CMB leading to the development of a compositional layering in the D″ layer. We speculate that there could be five layers of FeO-enriched melt from partial melting of MORB, MORB crust, anorthosite, TTG, and slab or mantle peridotite in ascending order. Although the polymorphic transformation of perovskite to post-perovskite in (Mg,Fe)SiO₃ may explain the seismic discontinuity at the top of the D″ layer (D″ discontinuity), the effects of solid solution on the sharpness of the transformation suggest that the compositional layering is more plausible for the origin of the D″ discontinuity. The D″ layer can be an “anti-crust” made up mostly of TTG + anorthosite derived from the former continental crust. Tectonic style of the anti-crust at the CMB is similar to that at the surface. At both places, chemically distinct layers are density stratified and are also characterized by the processes of accretion, magmatism, and metasomatism.     

Genesis modelling for the Hamersley BIF-hosted iron ores of Western Australia: a critical review

Enrichment iron ore of the Hamersley Province, currently estimated at a resource of over 40 billion tonnes (Gt), mainly consists of BIF (banded iron-formation)-hosted bedded iron deposits (BID) and channel iron deposits (CID), with only minor detrital iron deposits (DID). The Hamersley BID comprises two major ore types: the dominant supergene martite–goethite (M-G) ores (Mesozoic–Paleocene) and the premium martite–microplaty hematite ores (M-mplH; ca 2.0 Ga) with their various subtypes. The supergene M-G ores are not common outside Australia, whereas the M-mplH ores are the principal worldwide resource. There are two current dominant genetic models for the Hamersley BID. In the earlier 1980–1985 model, supergene M-G ores formed in the Paleoproterozoic well below normal atmospheric access, driven by seasonal oxidising electrochemical reactions in the vadose zone of the parent BIF (cathode) linked through conducting magnetite horizons to the deep reacting zone (anode). Proterozoic regional metamorphism/diagenesis at ～80–100°C of these M-G ores formed mplH from the matrix goethite in the local hydrothermal environment of its own exhaled water to produce M-mplH ores with residual goethite. Following general exposure by erosion in the Cretaceous–Paleocene when a major second phase of M-G ores formed, ground water leaching of residual goethite from the metamorphosed Proterozoic ores resulted in the mainly goethite-free M-mplH ores of Mt Whaleback and Mt Tom Price. Residual goethite is common in the Paraburdoo M-mplH-goethite ores where erratic remnants of Paleoproterozoic cover indicate more recent exposure.

Deep unweathered BIF alteration residuals in two small areas of the Mt Tom Price M-mplH deposits have been used since 1999 for new hypogene–supergene modelling of the M-mplH ores. These models involve a major Paleoproterozoic hydrothermal stage in which alkaline solutions from the underlying Wittenoom Formation dolomite traversed the Southern Batter Fault to leach matrix silica from the BIF, adding siderite and apatite to produce a magnetite–siderite–apatite ‘protore.’ A later heated meteoric solution stage oxidised siderite to mplH + ankerite and magnetite to martite. Weathering finally removed residual carbonates and apatite leaving the high-grade porous M-mplH ore. Further concepts for the Mt Tom Price North and the Southern Ridge Deposits involving acid solutions followed, but these have been modified to return essentially to the earlier hypogene–supergene model. Textural data from erratic ‘metasomatic BIF’ zones associated with the above deposits are unlike those of the typical martite–microplaty hematite ore bodies. The destiny of the massive volumes of dissolved silica gangue and the absence of massive silica aureoles has not been explained. Petrographic and other evidence indicate the Mt Tom Price metasomatism is a localised post-ore phenomenon. Exothermic oxidation reactions in the associated pyrite-rich black shales during post-ore removal by groundwater of remnant goethite in the ores may have resulted in this very localised and erratic hydrothermal alteration of BIF and its immediately associated pre-existing ore.     

VisualModflow模型在白涧铁矿区矿井涌水量预测中的应用

在分析确定白涧矿区水文地质边界条件的基础上,运用实测资料对Visu-almodflow模型进行识别和验证,同时修正了含水层的参数,修正后的模型较为可靠,可用于白涧矿区涌水量的预测。依据矿区奥灰含水层边界条件和渗透系数的不同,设计了-200m和-400m水平面不同边界及渗透系数三个方案对矿井的涌水量进行预测。结果表明:方案2的涌水量比较合理,能较真实的反映白涧铁矿矿体分布区水位疏降至-400m时的涌水量情况,预测其涌水量为7505m3/h。      

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.     

Depositional age and tectonic environment of the Gouap banded iron formations from the Nyong group,SW Cameroon:Insights from isotopic,geochemical and geochronological studies of drillcore samples

The discovery of the Gouap banded iron formations(BIFs)-hosted iron mineralization in the northwestern of the Nyong Group(Ntem Complex)in southwestern Cameroon provides unique insights into the geology of this region.In this contribution,we firstly report detailed study of geochemistry,isotopic and geochronology of well preserved samples of the Gouap BIFs collected from diamond drillcores.The Gouap BIFs consist mainly of amphibole BIFs and amphibole-pyrite BIFs characterized by dominant Fe₂O₃+SiO₂contents and variable contents of CaO,MgO and SO₃,consistent with the presence of amphibole,chlorite,epidote and pyrite,formed during amphibolite facies metamorphism and overprinted hydrothermal event.The amphibole–pyrite BIFs are typically enriched in trace and rare earth elements(REE)compared to the amphibole BIFs,suggesting the influence of detrital materials as well as secondary hydrothermal alteration.The Post Archean Australian Shale(PAAS)-normalized REE–Y profiles of the Gouap BIFs display positive La,Eu anomalies,weak negative Ce anomalies,indicating a mixture of low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.We present here the first isotopic data of BIFs within the Ntem Complex.Theδ³⁰Si_NBS28values of the quartz from the Gouap BIFs vary from-1.5‰to-0.3‰and from-0.8‰to-0.9‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.The quartz hasδ¹⁸OV-SMOW values of 6.8‰–9.5‰(amphibole BIFs)and 9.2‰–10.6‰(amphibole–pyrite BIFs).The magnetite from the Gouap BIFs showsδ¹⁸O values ranging from-3.5‰to-1.8‰and from-3‰to-1.7‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.Moreover,the pyrite grains in the amphibole–pyrite BIFs displayδ34S values of 1.1‰–1.8‰.All isotopic data of the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital input distant from the volcanic activity.According to their geochemical and isotopic characteristics,we propose that the Gouap BIFs belong to the Superior type.In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of zircon in thin section.The Gouap BIFs were probably deposited at 2422±50 Ma in a region where sediments extended from continental shelf to deep-water environments along craton margins like the Caue Formation of the Minas Supergroup,Brazil.The studied BIFs have experienced regional hydrothermal activity and metamorphism at 2089±8.3 Ma during the Eburnean–Transamazonian orogeny.These findings suggest a physical continuity between the protocratonic masses of both Sao Francisco and Congo continents in the Rhyacian Period.     

Influence of ferric iron on phase equilibria in greenschist facies assemblages: the hematite‐rich metasedimentary rocks from the Monti Pisani (Northern Apennines)

We have investigated the effects of different Fe₂O₃ bulk contents on the calculated phase equilibria of low‐T/intermediate‐P metasedimentary rocks. Thermodynamic modelling within the MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (MnNKFMASHTO) chemical system of chloritoid‐bearing hematite‐rich metasedimentary rocks from the Variscan basement of the Pisani Mountains (Northern Apennines, Italy) fails to reproduce the observed mineral compositions when the bulk Fe₂O₃ is determined through titration. The mismatch between observed and computed mineral compositions and assemblage is resolved by tuning the effective ferric iron content by P–XFe₂O₃ diagrams, obtaining equilibration conditions of 475 °C and 9–10 kbar related to a post‐compressional phase of the Alpine collision. The introduction of ferric iron affects the stability of the main rock‐forming silicates that often yield important thermobaric information. In Fe₂O₃‐rich compositions, garnet‐ and carpholite‐in curves shift towards higher temperatures with respect to the Fe₂O₃‐free systems. The presence of a ferric‐iron oxide (hematite) prevents the formation of biotite in the mineral assemblage even at temperatures approaching 550 °C. The use of P–T–XFe₂O₃ phase diagrams may also provide P–T information in common greenschist facies metasedimentary rocks.