Soldiers Cap Group iron‐formations,Mt Isa Inlier,Australia, as windows into the hydrothermal evolution of a base‐metal‐bearing Proterozoic rift basin

The Proterozoic Soldiers Cap Group, a product of two major magmatic rift phases separated by clastic sediment deposition, hosts mineralised (e.g. Pegmont Broken Hill‐type deposit) and barren iron oxide‐rich units at three main stratigraphic levels. Evaluation of detailed geological and geochemical features was carried out for one lens of an apatite‐garnet‐rich, laterally extensive (1.9 km) example, the Weatherly Creek iron‐formation, and it was placed in the context of reconnaissance studies of other similar units in the area. Chemical similarities with iron‐formations associated with Broken Hill‐type Pb–Zn deposit iron‐formations are demonstrated here. Concordant contact relationships, mineralogy, geochemical patterns and pre‐deformational alteration all indicate that the Soldiers Cap Group iron‐formations are mainly hydrothermal chemical sediments. Chondrite normalised REE patterns display positive Eu and negative Ce anomalisms, are consistent with components of both high‐temperature, reduced, hydrothermal fluid (≥250°C) and cool oxidised seawater. Major element data suggest a largely mafic provenance for montmorillonitic clays and other detritus during chemical sedimentation, consistent with westward erosion of Cover Sequence 2 volcanic rocks, rather than local mafic sources. Ni enrichment is most consistent with hydrogenous uptake by Mn‐oxides or carbonates. Temperatures inferred from REE data indicate that although they are not strongly enriched, base metals such as Pb and Zn are likely to have been transported and deposited prior to or following iron‐formation deposition. Most chemical sedimentation pre‐dated emplacement of the major mafic igneous sill complexes present in the upper part of the basin. Heating of deep basinal brines in a regional‐scale aquifer by deep‐seated mafic magma chambers is inferred to have driven development of hydrothermal fluids. Three major episodes of extension exhausted this aquifer, but were succeeded by a final climactic extensional phase, which produced widespread voluminous mafic volcanism. The lateral extent of the iron‐formations requires a depositional setting such as a sea‐floor metalliferous sediment blanket or series of brine pools, with iron‐formation deposition likely confined to much smaller fault‐fed areas surrounded by Fe–Mn–P–anomalous sediments. These relationships indicate that in such settings, major sulfide deposits and their associated chemical sediment marker horizons need not overlie major igneous sequences. Rather, the timing of expulsion of hydrothermal fluid reflects the interplay between deep‐seated heating, extension and magmatism.     

关于热水沉积物稀土配分模式的讨论

海底热水沉积物的稀土配分模式取决于流体的密度和流方式,低密度热流体的沉积物稀配合模式类似于海水模式,高密度热流体的沉积物没有固定的稀土配分模式,在判别热水沉积物时不宜单独使用稀土配分模式。     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

Rare earth element patterns in manganese nodules and micronodules from northwest Atlantic

The shale-normalized REE patterns of manganese nodules from the northwest Atlantic show enrichment in Sm and Eu relative to the heavier and lighter REE, excluding Ce, and are similar to the patterns previously observed in deep water (> 3000m) nodules from the Pacific. The inverse relation of this pattern to that of sea water and the high Ce anomaly (average 5.5) indicate that probably the REE in the nodules originate from sea water and the nodules are possibly hydrogenous. The patterns for micronodules are similar to those of the nodules but the concentrations of REE were substantially higher in two of them.The red clay occurring on abyssal hills where nodules and micronodules are found also shows higher REE concentrations over terrigenous gray clay. The latter is devoid of nodules and micronodules and occurs in abyssal plains. The excess REE in the red clay also show a pattern similar to those of the nodules and micronodules. Most of the micronodule samples show a lower Ce anomaly (1.7) and lower Co concentration compared to the nodules, so it is inferred that at least some micronodules were formed during post-depositional periods when the conditions were less oxidizing than average.     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

中元古界昆阳群因民组铁铜矿的成矿地球化学研究

因民组是川滇地区重要的铁铜矿赋存层位之一。系统地研究了因民组铁铜矿床的常量元素、微量元素、稀土元素、同位素和包裹体的特征，阐明成矿作用具有火山热水喷流－沉积成矿作用的地球化学特点。     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

Rare Earth Elements in Manganese Nodules from the Central Pacific Ocean

Manganese nodules in areas CP and CC of the central Pacific are rich in REE. Comparatively speaking,the REE contents of nodules in area CP are hihger than those in area CC; and the REE contents of nodulesfrom seamounts are higher than those of nodules from sea-floor plains and hills. Within the nodules, the REEshow a zonal distribution. The REE distribution patterns of the nodules are similar to those of the sedimentsand have a mirror image relationship with those of the sea water. Trivalent REE were not obviously differenti-ated when they entered into the nodules from the sea water.A major factor causing the difference of REE abundances between nodules and sediments is the redoxconditions. The redox intensity of the ocean floor of the Pacific is controlled mainly by Antarctic Bottom Wat-er(AABW), The iron-bearing facies in the nodules is the main carrier of REE.     

辽宁歪头山铁矿床两类矿石地球化学特征及其对成矿作用的制约

歪头山铁矿床是鞍山-本溪地区条带状铁建造（BIFs）的典型代表,并且有一定规模的富铁矿分布。本文主要报道了矿区内较贫铁矿石和较富铁矿石的地球化学特征,结果表明两类矿石既有一致性又存在差异性。一致性表现在：所有矿石主要由TFe2O3和SiO2组成,其他氧化物含量很少,结合微量元素和稀土元素特征,指示其为一种化学沉积岩,但受到了火山热液作用的影响;矿石的稀土元素总量很低,经太古界后平均澳大利亚页岩（PAAS）标准化后,呈现重稀土相对富集,轻稀土相对亏损的配分模式,都具有明显的Eu正异常,和比较高的Y/Ho比值,与热液相关的Cr、Co、Ni含量也相对较高,暗示其成矿物质来源于海底热液,同时具有海水的特征。差异性表现在：较富铁矿石具有明显的热液特征,并且K2O含量大于Na2O含量,某些微量元素组成也与混合花岗岩具有相似性,结合野外地质特征,暗示较富铁矿石可能是在较贫铁矿石的基础上受混合岩化热液作用形成的。     

煤系高岭岩的地球化学判别标志

本文主要研究了煤系高岭岩的微量、稀土、氧同位素地球化学特征。根据高岭岩产出层序、岩石学、矿物学、地球化学特征的研究，将煤系高岭岩分为两类：（１）铝土质高岭岩，微量元素含量、稀土总量，氧同位素值高，稀土配分模式与典型北美页岩相似，Ｅｕ负异常，反映其源岩为风化壳化学风化作用产物。（２）夹矸高岭岩，微量元素含量，稀土总量，氧同位素值低，稀土配分模式部分与典型北美页岩相似，反映其源岩与铝土质高岭岩类似；部     

海底热液沉积物稀土元素组成及其意义

总结了海底热液及其沉积物的稀土元素组成特征和控制因素。热水沉积物作为热液与海水混合的产物,其稀土元素组成及配分模式随海水混入的比例增加而发生一系列变化,反映了二端元流体不同混合程度的地球化学特征。Ｅｕ异常、Ｃｅ异常以及ｗ（Ｙ）／ｗ（Ｈｏ）比值是用来示踪古流体形成的物理化学环境及流体组成的重要参数。     

华南热水沉积硅质岩建造及其成矿效应

华南地区热水沉积建造发育。文中介绍该地区热水沉积建造 ,特别是震旦系顶部、泥盆系榴江组和二叠系当冲组 3个重要层位的硅质岩建造 ,分析它们的地质地球化学特征。研究表明 ,华南三层位沉积硅质岩的共同特征是TiO2 、Al2 O3 和K2 O含量一致偏低 ,大部分微量元素含量偏低 (与地壳克拉克值相比 ) ,但Ba、As、Sb富集 ,具有较为典型的热水沉积成因特点。多元统计分析显示 ,大部分微量元素在第一个主因子上均有显著因子载荷 ,与它们在基底的富集或亏损无关 ,代表了古地热系热水循环中的淋滤因子。华南三层位热水成因硅质岩具有相似的REE地球化学特征。REE总量低 ,稀土配分模式落在典型热水沉积物的上、下限之间 ,多数样品呈现δCe和δEu负异常。正常沉积的混入使部分硅质岩的REE配分模式复杂化。最后 ,讨论了与热水沉积建造相关的成矿效应 ,为金属矿床成因和评价提供约束条件     

长江与黄河沉积物稀土元素随粒度变化对比研究

依据Stoke定律将长江小于63 μm的沉积物分成4个粒级.将黄河小于63 μm的沉积物分成6个粒级.采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示：相同粒级中长江沉积物的∑REE均高于黄河沉积物.长江沉积物REE的丰度遵循元素的“粒度控制律”,即随粒度变细∑REE含量依次增高;黄河沉积物∑REE呈“高-低-高”的不对称马鞍型分布;北美页岩标准化分布曲线均呈右倾状,轻重稀土分馏明显,相对富集LREE,具弱Ce亏损,明显的Eu正异常.长江与黄河沉积物REE组成特征差异与两条河流流域的风化作用及沉积物的矿物组成密切相关,黄河∑REE的马鞍型分布是细粒级中黏土矿物吸附及粗粒级中相对高含量的重矿物富集作用的结果,而长江沉积物随粒级增大∑REE的衰减趋势主要是随粒级增大逐步增加的石英和长石含量的稀释作用所造成.     

Apatite nodules as an indicator of depositional environment and ore genesis for the Mesoproterozoic Broken Hill-type Gamsberg Zn–Pb deposit,Namaqua Province,South Africa

Nodules consisting of fluorapatite are concentrated as a discrete band in the polymetallic sulfide ore of the Gamsberg deposit in central Bushmanland, South Africa. Their shape, zonal features, and geochemistry, in particular rare earth element (REE) abundances, are similar to authigenic francolite concretions that precipitate during diagenesis in organic-rich muds. As a result, the apatite nodules are regarded as primary. The nodules have a strong lithostratigraphic control, occurring at the transition of siliciclastic-hosted pyrite–sphalerite–graphite mineralization to calc-silicate-hosted pyrrhotite–sphalerite mineralization. Mineralogical and chemical evidence indicates that this transition also corresponds to a paleo-redox boundary that separates sediments deposited under oxygen-deficient conditions from those that developed in a more oxygenated environment. The apatite nodules can morphologically and chemically clearly be distinguished from coarse apatite grains that occur in oxide-facies iron formations stratigraphically above the ore horizon. However, similar REE profiles and in particular positive Eu anomalies in both types of apatite are indicative of a close genetic relationship between the two units and favor a common hydrothermal origin of the P. The contrasting morphologies and chemical signatures of the two occurrences can rather be attributed to differences in behavior of the phosphates during precipitation within the contrasting host sediments (chemical versus fine-grained clastic). Taking modern phosphorites as an analogue, these results are used to postulate a genetic model for the deposition of the sulfide ore and associated iron formations. The model envisages differentiation of the depositional basin into oxygen-deficient basin facies hosting the sulfide ore and oxygenated shelf facies, which are composed of manganiferous iron formations. The intimate association of sedimentary apatite with base metal sulfides indicates that basin conditions were conducive to the precipitation of both phases. This relationship might act as a potential exploration guide in similar basins elsewhere.Editorial handling: E. Frimmel     

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.     

Geochemistry of Apatite from the Apatite-rich Iron Deposits in the Ningwu Region, East Central China

Four types of apatite have been identified in the Ningwu region.The first type of apatite is widely distributed in the middle dark colored zones(i.e.iron ores) of individual deposits.The assemblage includes magnetite,apatite and actinolite(or diopside).The second type occurs within magnetite-apatite veins in the iron ores.The third type is seen in magnetite-apatite veins and (or) nodules in host rocks(i.e.gabbro-diorite porphyry or gabbro-diorite or pyroxene diorite).The fourth type occurs within apatite-pyrite-quartz veins filling fractures in the Xiangshan Group.Rare earth elements (REE) geochemistry of apatite of the four occurrences in porphyry iron deposits is presented.The REE distribution patterns of apatite are generally similar to those of apatites in the Kiruna-type iron ores,nelsonites.They are enriched in light REE,with pronounced negative Eu anomalies.The similarity of REE distribution patterns in apatites from various deposits in different locations in the world indicates a common process of formation for various ore types,e.g. immiscibility.Early magmatic apatites contain 3031.48-12080×10~(-6) REE.Later hydrothermal apatite contains 1958×10~(-6) REE,indicating that the later hydrothermal ore-forming solution contains lower REE.Although gabbro-diorite porphyry and apatite show similar REE patterns,gabbro-diorite porphyries have no europium anomalies or feeble positive or feeble negative europium anomalies, caused both by reduction environment of mantle source region and by fractionation and crystallization(immiscibility) under a high oxygen fugacity condition.Negative Eu anomalies of apatites were formed possibly due to acquisition of Eu~(2+) by earlier diopsite during ore magma cooling. The apatites in the Aoshan and Taishan iron deposits yield a narrow variation range of ~(87)Sr/~(86)Sr values from 0.7071 to 0.7073,similar to those of the volcanic and subvolcanic rocks,indicating that apatites were formed by liquid immiscibility and differentiation of intermediate and basic magmas.     

Excess europium content in precambrian sedimentary rocks and continental evolution

We propose that the europium excess in Precambrian sedimentary rocks, relative to those of younger age is derived from volcanic rocks of ancient island arcs, which were the source materials for the sediments. Precambrian sedimentary rocks and present-day volcanic rocks of island arcs have similar REE patterns, total REE abundances and excess Eu, relative to the North American shale composite. The present upper crustal REE pattern, as exemplified by that of sediments, is depleted in Eu, relative to chondrites. This depletion is considered to be a consequence of development of a grandioritic upper crust by partial melting in the lower crust, which selectively retains europium.     

Preliminary study of REE iron formations in China

Geological and geochemical characteristics of REE iron formation (REEIF), a term proposed by Prof. Tu Kuang-chih to specify a special type of Precambrian iron formations rich in REE, are discussed in this paper with special reference to its REE contents, REE distribution patterns, the formation mechanism, the relationship between its development and the multi-stage evolution of the continental crust in China, and the implications of REE as an indicator of oxidation state for ancient atmosphere. Major conclusions are outlined as follows:

1. REEIFs are characterized by high REE concentrations against the very low REE levels in normal Precambrian iron formations.
2. REEIFs are formed by marine sedimentary-diagenetic processes in miogeosynclines or transition zones during Proterozoic times To some extent, volcanic activity may play an important role in the deposition of ore-forming materials. In a broader sense, REEIFs belong to Fe-bearing dolomite formations. Most REEIFs in China may be superimposed by late geological processes such as hydrothermal-metasomatism, migmatization and metamorphism. Generally, REEIFs have much in common with stratabound ore deposits in respect to their characteristic features.
3. Similar to Precambrian iron formations, REE are enriched in LREE. But, the degree of LREE enrichment is noticed to increase of total REE content. Most REEIFs are characterized by high ratios of σ Ce/σY, (Mg+Fe)/Ca, Na/K, Nb/Ta, Zr/Hf, Th/U, Ba/Sr, etc.
4. The extensive occurrence of REEIFs indicates higher REE abundance in the continental crust of China, thus lending further support to the multi-stage theory regarding the evolution of chemical elements and the differentiation in the continental crust of China.
5. Preliminary data seem to support the time-dependence of REE distribution patterns and relative Eu contents of REEIFs in China.

     

长江与黄河沉积物REE地球化学及示踪作用

长江与黄河沉积物的稀土元素（ＲＥＥ）组成特征不同。长江沉积物ＲＥＥ含量较高,元素含量变化也大于黄河样品;球粒陨石标准化模式表明长江沉积物的（Ｌａ／Ｌｕ）Ｎ、（Ｌａ／Ｙｂ）Ｎ、（Ｇｄ／Ｙｂ）Ｎ的值也相应地比黄河沉积物中的高１０％左右,分布曲线均呈明显的石倾状,轻重稀土分馏明显,相对富集ＬＲＥＥ。且长江样品比黄河样品更富集ＬＲＥＥ,但Ｅｕ亏损不及黄河样品;两者的北美页岩标准化曲线均呈平坦稍右倾状,具有     

冀东南地区稀土元素演化特征及基准值研究

从冀东南地区系统采集了地表水(n=37)、地下水(n=31)、水系沉积物(n=81)、土壤(n=242)和岩石(n=472)的稀土样品,利用统计学和岩性岀露加权方法分别对14个稳定的稀土元素(REE)含量及各类稀土基准值和分布模式方面进行了研究。对岩石—土壤—水系沉积物—地下水和地表水系统中稀土元素迁移和分布模式的研究表明,随土壤的发育,REE出现富集,并出现分异,HREE比LREE更易在土壤中富集;Eu在岩石和土壤中由负异常到地下水和地表水的正异常演化特征。地表水和地下水中REE的含量和分布模式相近。