Uranium in supergene phosphorites

The distribution of uranium was studied in supergene phosphorites from the zones of the weathering of sedimentary and endogenous rocks, as well as in nonmarine coprolitic phosphorites and, to a lesser extent, phosphorites from ocean islands. These phosphorites show a diversity of the composition of their carbonate-apatite and structural characteristics. The uranium content ranges mostly from 5 to 100 ppm, with minimum and maximum values of 0.5 and 790 ppm. There is no correlation between the uranium content of a phosphorite and the type of rock with which it is connected. Lacustrine coprolitic phosphorites show elevated uranium contents (about 200 ppm). The maximum uranium content was detected in finely laminated phosphorite encrustations. The correlation analysis of the whole data set (63 samples) showed that uranium content is not correlated with any other component of phosphorites at a confidence level of 0.95. In contrast, there is a correlation between U and P₂O₅, CaO, and F for the combined set of samples from southern Siberian deposits. The significant correlation of U with Na₂O and CO₂ is variable both for southern Siberia on the whole and for particular deposits from this region.     

Trace elements in supergene phosphorites

Supergene phosphorites were analyzed for Sr, Ba, Zn, Cd, Sc, Cr, Ag, and V, i.e., elements incorporated in carbonate-apatite by isomorphic substitution. The phosphorites were subdivided into four groups: (1) phosphorites related to the weathering of sedimentary rocks, (2) phosphorites related to the weathering of endogenous rocks, (3) lacustrine coprolite phosphorites, and (4) phosphorites of ocean islands. In all the phosphorites groups, Sr, Zn, and Ba were the most abundant of the trace elements, whereas Cd, Ag, and Sc showed the lowest concentrations. Variations in trace element contents between supergene phosphorites of different genetic groups or within a single group can be explained by the different compositions of weathered rocks and geochemical environments of supergene phosphorite formation. At the same time, the contents of some trace elements are correlated with the structural type of phosphorite. In particular, phosphorite crusts or only their outer parts show elevated contents of chalcophile elements (Cd, Zn, and Ag), whereas massive phosphorites and inner parts of crusts are often enriched in such lithophile elements as Sc, V, and Cr. It was found that Cd, Zn, Ag, Sr, and Ba are positively correlated with CO₂ but show negligible correlations with other constituents of carbonate-apatite.     

Reconstruction of phosphate formation environments (from data on distribution of lanthanides)

The criteria for the evaluation of the REE composition of phosphorites and sedimentary rocks have been determined. These data are required to reconstruct depositional environments. Literature data on the geochemistry of some phosphorite deposits of Eurasia are considered. The REE patterns of Mesozoic phosphorites of the East European Platform are studied. On the basis of REE contents, the ratios of lanthanides and fields on the La–(Nd + Sm)–(Y + Dy), La–(Ce + Nd + Sm)–(Y + Dy), and LREE–MREE–(HREE×10) diagrams have been determined as indicators of climate and the depth and facies conditions of sedimentation.     

Metavolcanic host rocks,mineralization, and gossans of the Shaib al Tair and Rabathan volcanogenic massive sulphide deposits of the Wadi Bidah Mineral District,Saudi Arabia

The Wadi Bidah Mineral District of Saudi Arabia contains more than 16 small outcropping stratabound volcanogenic Cu–Zn–(Pb) ± Au-bearing massive sulphide deposits and associated zones of hydrothermal alteration. Here, we use major and trace element analyses of massive sulphides, gossans, and hydrothermally altered and least altered metamorphosed host rock (schist) from two of the deposits (Shaib al Tair and Rabathan) to interpret the geochemical and petrological evolution of the host rocks and gossanization of the mineralization. Tectonic interpretations utilize high-field-strength elements, including the rare earth elements (REE), because they are relatively immobile during hydrothermal alteration, low-grade metamorphism, and supergene weathering and therefore are useful in constraining the source, composition, and physicochemical parameters of the primary igneous rocks, the mineralizing hydrothermal fluid and subsequent supergene weathering processes. Positive Eu anomalies in some of the massive sulphide samples are consistent with a high temperature (>250°C) hydrothermal origin, consistent with the Cu contents (up to 2 wt.%) of the massive sulphides. The REE profiles of the gossans are topologically similar to nearby hydrothermally altered felsic schists (light REE (LREE)-enriched to concave-up REE profiles, with or without positive Eu anomalies) suggesting that the REE experienced little fractionation during metamorphism or supergene weathering. Hydrothermally altered rocks (now schists) close to the massive sulphide deposits have high base metals and Ba contents and have concave-up REE patterns, in contrast to the least altered host rocks, consistent with greater mobility of the middle REE compared to the light and heavy REE during hydrothermal alteration. The gossans are interpreted to represent relict massive sulphides that have undergone supergene weathering; ‘chert’ beds within these massive sulphide deposits may be leached wall-rock gossans that experienced silicification and Pb–Ba–Fe enrichment from acidic groundwaters generated during gossan formation.     

广西某地花岗岩风化壳中稀土元素特征与iREE矿床成矿机制

为了解风化壳中离子交换相稀土元素的特征,对广西某地花岗岩风化壳剖面样品进行了X射线衍射及主量、稀土元素地球化学特征的研究.剖面自上而下可划分为腐殖土层(A₁)、亚粘土层(A₂)、网纹状风化层(B₁)和全风化层(B₂);自A₁至B₂,粘土矿物的含量和化学风化蚀变指数快速降低;与母岩相比A₁、A₂、B₁中全相Ce、Nd和HREE相对富集,B₂中全相稀土与母岩特征相似,所有样品的离子交换相HREE亏损,Y相对富集;离子交换相轻、重稀土一起富集在B₂中.据此推测,花岗岩中褐帘石、榍石等易风化的稀土矿物为离子交换相稀土提供了主要的物源,锆石、磷钇矿等难风化的稀土矿物的残留及表生稀土矿物的形成使全相HREE相对富集;离子交换相轻、重稀土元素的分馏程度随风化程度的增加而变化.      

Trace elements and REE fractionation in subsoils developed on sedimentary and volcanic rocks: case study of the Mt. Vulture area,southern Italy

There is an increasing interest in the distribution of rare earth elements (REEs) within soils, primarily as these elements can be used to identify pedogenetic processes and because soils may be future sources for REE extraction, despite much attention should be paid to the protection and preservation of present soils. Here, we evaluate the processes that control the distribution of REEs in subsoil horizons developed over differing lithologies in an area of low anthropogenic contamination, allowing estimates of the importance of source rocks and weathering. Specifically, this study presents new data on the distribution of REEs and other trace elements, including transition and high-field-strength elements, in subsoils developed on both Quaternary silica-undersaturated volcanic rocks and Pliocene siliciclastic sedimentary rocks within the Mt. Vulture area of the southern Apennines in Italy. The subsoils in the Mt. Vulture area formed during moderate weathering (as classified using the chemical index of alteration) and contain an assemblage of secondary minerals that is dominated by trioctahedral illite with minor vermiculite. The REEs, high-field-strength elements, and transition metals have higher abundances in subsoils that developed from volcanic rocks, and pedogenesis caused the Mt. Vulture subsoils to have REE concentrations that are an order of magnitude higher than typical values for the upper continental crust. This result indicates that the distribution of REEs in soils is a valuable tool for mineral exploration. A statistical analysis of inter-elemental relationships indicates that REEs are concentrated in clay-rich fractions that also contain significant amounts of low-solubility elements such as Zr and Th, regardless of the parent rock. This suggests that low-solubility refractory minerals, such as zircon, play a significant role in controlling the distribution of REEs in soils. The values of (La/Yb)_N and (Gd/Yb)_N fractionation indices are dependent on the intensity of pedogenesis; soils in the study area have values that are higher than typical upper continental crust ratios, suggesting that soils, especially those that formed during interaction with near neutral to acidic organic-rich surface waters, may represent an important source of both light REEs and medium REEs (MREEs). In comparison, MREE/heavy REE fractionation in soils that form during moderate weathering may be affected by variations in parent rock lithologies, primarily as MREE-hosting minerals, such as pyroxenes, may control (La/Sm)_N index values. Eu anomalies are thought to be the most effective provenance index for sediments, although the anomalies within the soils studied here are not related to the alteration of primary minerals, including feldspars, to clay phases. In some cases, Eu/Eu* values may have a weak correlation with elements hosted by heavy minerals, such as Zr; this indicates that the influence of mechanical sorting of clastic particles during sedimentary transport on the Eu/Eu* values of siliciclastic sediments needs to be considered carefully.     

贵州瓮安陡山沱组磷块岩稀土元素地球化学特征与沉积期后变化

贵州瓮安陡山沱组磷块岩保存了可能是全球最早的后生动物化石 (瓮安动物群 ),对于瓮安动物群出现过程中的古海洋环境重建具有重要科学意义。但必须对成岩后生作用对磷块岩中的稀土元素改造进行评估。通过对贵州瓮安陡山沱组磷块岩的磷质碎屑、磷质和白云质胶结物、磷条带和泥条带等的稀土元素地球化学特征研究,确定沉积期后变化对稀土元素的改造影响不大。上矿层磷块岩沉积期形成的磷质碎屑、成岩期形成的白云质和磷质胶结物具相同的稀土元素配分模式,暗示了沉积期后的改造作用对瓮安陡山沱组磷块岩保存的原生沉积信息影响不大。瓮安陡山沱组磷块岩具有显著的重稀土亏损特征。磷块岩的磷质和白云质胶结物、伴生磷质碎屑、强风化磷块岩相近的ErN/LuN 比值,表明沉积期后的改造作用不是重稀土元素亏损的主要原因。磷块岩的ErN/LuN、LaN/NdN 与Ce/Ce 间的相关性,表明越氧化的沉积环境中,轻和重稀土元素亏损越强。     

荆襄地区陡山沱组磷块岩的类型、成因和沉积环境

本文根据野外调查和室内初步研究成果并结合有关地质资料,分析、讨论了荆襄陡山沱组含磷岩系的磷块岩类型、成因和沉积环境。通过分析可知,组成磷块岩的磷灰石有不同的形成方式;磷块岩沉积在海退旋回中粘土和硅质沉积向碳酸盐沉积的转变阶段;磷块岩矿床形成在陆缘海内与深水有联系的浅水地带。 矿区含磷岩系特征综合于图1。     

陕南天台山、茶店一带磷块岩的时代和成因特征

陕西南部汉中天台山、勉县茶店和略阳何家岩、金家河一带磷块岩的时代,目前有三种看法,即:泥盆纪、震旦纪和寒武纪。这一带磷块岩的成因也比较复杂。在磷酸盐沉积、成岩以后,又受到变质、褶皱、断裂和水溶液活动影响。本文对天台山、茶店一带的磷块岩的成矿时代和生成特点提出一些初步意见。     

Precambrian phosphorites in the Bijawar rocks of Hirapur-Bassia areas,sagar district,madhya pradesh,India

The Precambrian phosphorites of Bijawar Group of rocks show characteristics of a epicontinental sea with restricted and very shallow marine environment of formation along some shoals, which existed during the iron-rich Precambrian times. These phosphorite deposits located in the Hirapur-Bassia areas show extensive leaching of carbonate and phosphate minerals during episodes of weathering. X-ray diffraction studies indicated that carbonate-flourapatite is the major apatitic phase in these phosphorites while crandallite developed on the surface outcrops. There is a general tendency for the depletion of CO₂ in these apatites leading to formation of flourapatite. This CO₂ is an indicator of hidden weathering in the rocks. Major and trace element determinations of phosphorite have been used to indicate various correlation factors responsible for the concentration of elements in these Precambrian leached phosphorites.The paper is a contribution to the aims and objectives of IGCP Project 156The paper is dedicated to Prof. Dr. R. C. Misra, who as a teacher and guide had been a source of inspiration to the senior author for the last two decades     

山东灵山岛莱阳群粉砂岩地球化学特征及意义

灵山岛下部莱阳群重力流沉积地层以其巨厚的沉积规模,独特的沉积特征受到国内外地质学界越来越多的重视.但目前,该套地层的源区风化程度、物源性质、物源区构造背景及沉积环境尚不明确,通过对灵山岛下部莱阳群粉砂岩进行岩相学分析、主量元素XRF测试、稀土及微量元素ICP-MS测试,结果显示:粉砂岩SiO₂含量较低 (平均51.78%),Fe₂O₃T含量较高 (平均5.73%),Na₂O平均含量为2.74%,K₂O平均含量为2.79%;通过主量元素投图分析,样品归类为杂砂岩及岩屑砂岩;样品ΣREE为153.00×10-6~254.38×10-6,平均为201.65×10-6,高于PAAS及UCC,富集轻稀土元素,贫重稀土元素,具有中等程度Eu负异常,弱Ce负异常;相对于UCC,样品富集大离子亲石元素,弱富集高场强元素,亏损过渡组元素.样品ICV值高 (＞0.84)、为初次循环沉积,CIA值低 (＜65) 表明源区风化强度低,物源为长英质物质及少量古地壳再旋回物质,物源区大地构造背景为大陆岛弧与活动大陆边缘,沉积环境为海相还原环境且莱阳期为干热气候.此外,应用对REE元素进行归类统计的方法来推测物源区,分析表明样品物源区最有可能为胶南群与蓬莱群地层.      

The supergene thorium and rare-earth element deposit at Morro do Ferro, Poços de Caldas, Minas Gerais, Brazil

The thorium and rare-earth element (Th-REE) deposit at Morro do Ferro formed under supergene lateritic weathering conditions. The ore body consists of shallow NW-SE elongated argillaceous lenses that extend from the top of the hill downwards along its south-eastern slope. The deposit is capped by a network of magnetite layers which protected the underlying highly weathered, argillaceous host rock from excessive erosion. The surrounding country rocks comprise a sequence of subvolcanic phonolite intrusions that have been strongly altered by hydrothermal and supergene processes.From petrological, mineralogical and geochemical studies, and mass balance calculations, it is inferred that the highly weathered host rock was originally carbonatitic in composition, initially enriched in Th and REEs compared to the surrounding silicate rocks. The intrusion of the carbonatite caused fenitic alteration in the surrounding phonolites, consisting of early potassic alteration followed by a vein-type Th-REE mineralization with associated fluorite, carbonate, pyrite and zircon. Subsequent weathering has completely decomposed the carbonatite forming a residual supergene enrichment of Th and REEs.Initial weathering of the carbonatite has created a chemical environment that might have been conductive to carbonate and phosphate complexing of the REEs in groundwaters. This may have appreciably restricted the dissolution of primary REE phases. Strongly oxidic weathering has resulted in a fractionation between Ce and the other light rare earth elements (LREEs). Ce³⁺ is oxidized to Ce⁴⁺ and retained together with Th by secondary mineral formation (cerianite, thorianite), and by adsorption on poorly crystalline iron- and aluminium-hydroxides. In contrast, the trivalent LREEs are retained to a lesser degree and are thus more available for secondary mineral formation (Nd-lanthanite) and adsorption at greater depths down the weathering column. Seasonally controlled fluctuations of recharge waters into the weathering column may help to explain the observed repetition of Th-Ce enriched zones underlain by trivalent LREE enriched zones.     

黔中陡山沱期磷块岩成因的系统研究

黔中成磷区是中国南方陡山沱成磷期磷块岩矿床的重要组成部分。包括瓮福、开阳两个大型磷块岩矿床和若干中小型磷矿床。本文从磷的来源、沉积和富集3个方面系统地揭示了该区磷块岩的成因。稀土元素分析表明,磷可能来自同期海底火山喷发物。海洋地球化学、生物化学及磷块岩的组构研究证明,藻类生物的吸收和固定作用是磷质沉积的主要途径。磷的富集的多阶段、多因素的,经历不同的富集阶段(或方式)形成不同的磷块岩类型。     

贺兰山地区晚三叠世延长组地球化学特征及其地质意义

沉积岩的微量和稀土元素对沉积环境变化有着较高的灵敏度,是研究古沉积环境以及沉积物源区构造背景的一种有效手段。本文主要利用地球化学方法对贺兰山晚三叠世延长组不同地区、不同层段的25件泥岩、粉砂岩以及细砂岩样品进行了主量、微量以及稀土元素测试分析,探讨了延长期沉积环境和物源区构造背景。结果显示：延长期整体处于氧化—还原过渡的淡水环境,古气候温暖潮湿;稀土元素球粒陨石标准化配分表现为轻重稀土分异明显,且轻稀土富集、重稀土相对亏损,Eu负异常,Ce异常不明显等特征;La/Yb-REE和La/Th-Hf源岩判别图及Gd/Yb的比值关系图显示延长组源岩主要为长英质岩石,部分为基性岩和沉积岩,且以后太古界为主要物源;La-Th-Sc,Th-Sc-Zr/10和Th-Co-Zr/10判别图解均显示研究区延长组物源区构造背景主要为大陆岛弧,晚期有活动陆缘构造背景的物源加入。     

山西西铭煤矿煤中稀土元素地球化学特征及指示意义

采用电感耦合等离子体质谱(ICP-MS)及X射线荧光光谱(XRF)等方法,分析山西西铭煤矿2号、3号、8 号和9号煤中稀土元素的含量特征和赋存状态,并根据稀土元素Ce、Eu、Gd、Y和常量元素Al₂O₃/TiO₂的异常揭示其成煤环境及物质来源。研究结果显示:(1)西铭煤矿煤中稀土元素含量与世界煤值和美国煤值基本相等,但低于中国煤中稀土元素含量的平均值;稀土元素以中-重稀土富集型为主,其次是轻稀土富集型和轻-中稀土富集型。(2)西铭煤矿成煤环境总体上以弱还原性为主,且受酸性沼泽水环境影响。(3)煤中稀土元素的物质来源主要为陆源碎屑物质,判断其沉积源岩为酸性或中-酸性岩浆岩。     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

朝阳磷矿磷块岩的类型和成因特征

朝阳磷矿的磷块岩有五种类型,即泥晶磷块岩、球粒磷块岩、鲕粒磷块岩、内碎屑磷块岩和细晶磷块岩。其中内碎屑磷块岩占优势。磷酸盐岩沉积在海退旋回中,是处于深水向浅水过渡的层位。磷块岩的沉积环境主要是隆起附近的浅水带。     

中国东部大陆尺度地球化学走廊带碳酸盐岩稀土元素分布特征与影响因素

碳酸盐岩是地球表层岩石圈的重要组成部分,其化学组成可提供沉积环境与海洋水体演化等信息,然而,前人对碳酸盐岩中稀土等元素的分布与变化特征关注不足。本文选择穿越中国东部6个一级大地构造单元的3条地球化学走廊带,系统采集了582件碳酸盐岩地层样品,并准确分析了包括稀土元素(REE)在内的81项指标的含量。结果表明,中国东部地球化学走廊带碳酸盐岩稀土元素(REE＋Y)总量为(0.59～183)×10-6,均值为24.0×10-6,纯净碳酸盐岩(CMC含量≥99％)均值为4.80×10-6。PAAS标准化后其显示具有轻稀土相对于中稀土和重稀土略亏损、δEu轻微正异常、δCe中度负异常等特征。白云岩中稀土含量、LREE/HREE值一般低于石灰岩;砂泥质含量相近时,前中生代各时代碳酸盐岩稀土分布模式相差不大,各构造单元稀土分布特征基本相似;与其他时代相比,中生代及中新元古代碳酸盐岩具有相对较平坦的稀土分布模式。研究表明,碳酸盐岩中稀土分布受碎屑物质影响明显,表现为稀土元素含量与碳酸根负相关,与碎屑物质相关元素(Si、Ti、Rb、Cs、Th、Zr等)、黏土相关元素(Al、Fe、K等)等正相关。成岩过程及白云化过程对较纯净碳酸盐岩中稀土分布特征影响不明显。我国古生代纯净碳酸盐岩分布模式受控于海相环境,其分布模式与现今海水相近;中生代纯净石灰岩受到陆相或海陆交互相的影响,具有较平坦的稀土分布模式。氧化还原条件对δCe的影响较δEu更为明显,δCe值受海相环境控制,极端正异常值(δCe＞1.3)受到还原环境或/和热液影响。若假定海水中REE自中元古代至今无太大变化,各时代稀土元素分配系数均值介于103.55～102.39,分配系数差异是造成碳酸盐岩中轻稀土亏损、Ce负异常及Y正异常的主要原因。微生物(席)可富集稀土等金属元素并改变沉积环境,这可能是造成中新元古界碳酸盐岩较平坦的稀土分布模式的主要原因。     

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