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1.
The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO2, Al2O3, P2O5 and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.  相似文献   

2.
Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.  相似文献   

3.
The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al2O3 and TiO2, SiO2, K2O, and Na2O, and strong negative correlations between Al2O3 and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K2O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ13C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO3? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.  相似文献   

4.
浙江八面山萤石矿床稀土元素地球化学特征及成因探讨   总被引：4，自引：2，他引：2  
对浙江八面山萤石矿床中不同类型萤石矿石和围岩样品的稀土元素的系统分析表明,细粒萤石矿石的ΣREE〈39×10-6,LREE为14.36×10-6～34.24×10-6,HREE0.96×10-6～2.04×10-6,Y〈3×10-6;巨晶萤石矿石中的ΣREE3.62×10-6～20.81×10-6,LREE2.71×10-6～17.67×10-6,HREE0.24×10-6～1.49×10-6;而围岩花岗岩的ΣREE460.29×10-6,LREE225.97×10-6,HREE91.32×10-6,Y＆gt;140×10-6;沉积岩中的ΣREE20.22×10-6、LREE16.11×10-6、HREE1.61×10-6。矿石与围岩中沉积岩的稀土总量、轻稀土、重稀土和Y的含量接近,与花岗岩的稀土总量、轻稀土、重稀土和Y元素含量相差悬殊。萤石矿石的稀土分布型式主要为轻稀土富集型,（La/Yb）N通常多数大于8,在8.07～17.26间,δEu值在0.45～1.30,δCe在0.89～1.14间,Ce、Eu基本不显异常。矿石与围岩的稀土地球化学研究显示,八面山萤石矿床为受地层、岩体与断裂共同控制＂三位一体＂的低温热液型矿床。  相似文献   

5.
The ΣREE and shale-normalized (PAAS) REESN 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 REESN 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 REESN 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 REESN 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 REESN 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 REESN trends relative to that in bLMC of their preserved counterparts. Similarly, the ΣREE and REESN 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 REESN 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 REESN 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 REESN 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 REESN trends. The overall enrichment or depletion of the cement REESN 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.  相似文献   

6.
Major, trace and rare earth elements (REE) concentration of the Eocene limestones, Jaisalmer Basin, Rajasthan, India are analysed to reconstruct the depositional conditions and to identify sources of REEs. Among the major oxides, CaO is the dominant oxide followed by SiO2 in the studied limestones. Trace element Ba dominates over the other trace elements and it shows negative correlation with CaO. The Sr, occurring in small concentration, shows positive correlation with CaO. Other trace elements such as V, Zr, Sc, Y, Rb, Ni, Pb Co, Cu, U occur in small concentrations. The studied limestones show a positive correlation of ΣREE with Fe2O3, Ni, Th, Sc, and Y. These limestones possess sea-water like shale-normalized REE + Y pattern with light REE depletion, slight Gd enrichment, slightly positive La anomaly, positive Y anomaly, positive Eu anomaly, negative Ce anomaly and superchondritic Y/Ho ratio from 23.12 to 28.57. The dominance of CaO and low percentage of MgO suggest that mineral phase is calcite and there is absence of dolomitization. The occurrence of SiO2 and Al2O3 in appreciable percentages may be because of the siliciclastic input during the limestone precipiatetion. The low concentration of Uranium (0.4-3.7) and authigenic Uranium (Average Total U-Th/3 value = 0.74) indicate that the studied limestones were precipitated in oxic condition from seawater. The depletion of LREE suggests that the limestones were precipitated from the seawater. The positive correlation of ΣREE with Al2O3 Fe2O3, Ni, Th, Sc, and Y and negative correlation with CaO suggest an input of siliciclastic sediments from the land during limestone precipitation. The negative Ce anomaly, slightly positive La anomaly, slight Gd enrichment, positive Y anomaly, and positive Eu anomaly also suggest that the limestone was precipitated from the seawater with some siliciclastic input from continent. The low values of the Y/Ho ratio (23.12 to 28.57) in the studied limestones suggest some modification of the seawater by the input of freshwater in a coastal environment. The REEs of the studied limestones are correlable with the shallow sea water REEs with exception of a few elements. We envisage a coastal/shallow marine depositional environment where mixing of the continental material in sea water appears feasible.  相似文献   

7.
The Bijgan barite deposit, which is located northeast of Delijan in Markazi Province of Iran, occurs as a small lenticular body at the uppermost part of an Eocene volcano-sedimentary rock unit. The presence of fossiliferous and carbonaceous strata suggests that the host rocks were deposited in a quiet marine sedimentary environment. Barite, calcite, iron oxides and carbonaceous clay materials are found as massive patches as well as thin layers in the deposit. Barite is marked by very low concentrations of Sr (1–2%) and total amounts of rare earth elements (REEs) (6.25–17.39?ppm). Chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (LREEs) from La to Sm, similar to those for barite of different origins from elsewhere. The LaCN/LuCN ratios and chondrite-normalized REE patterns reveal that barite in the Bijgan deposit is enriched in LREE relative to heavy rare earth elements (HREEs). The similarity between the Ce/La ratios in the barite samples and those found in deep-sea barite supports a marine origin for barite. Lanthanum and Gd exhibit positive anomalies, which are common features of marine chemical sediments. Cerium shows a negative anomaly in most samples that was inherited from the negative Ce anomaly of hydrothermal fluid that mixed with seawater at the time of barite precipitation. The δ18O values of barites show a narrow range of 9.1–11.4‰, which is close to or slightly lower than that of contemporaneous seawater at the end of the Eocene. This suggests a contribution of oxygen from seawater in the barite-forming solution. The δ34S values of barites (9.5–15.3‰) are lower than that of contemporaneous seawater, which suggests a contribution of magmatic sulfur to the ore-forming solution. The oxygen and sulfur isotope ratios indicate that submarine hydrothermal vent fluids are a good analog for solutions that precipitated barite, due to similarities in the isotopic composition of the sulfates. The available data including tectonic setting, host rock characteristics, REE geochemistry, and oxygen and sulfur isotopic compositions support a submarine hydrothermal origin for the Bijgan barite deposit. At the seafloor, barite deposition occurred where ascending Ba-bearing hydrothermal fluids encountered seawater. Sulfate was derived from the sulfate-bearing marine waters, and, to a lesser extent, by oxidized H2S, which was derived from magmatic hydrothermal fluids.  相似文献   

8.
The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al2O3, SiO2, Fe2O3 and TiO2 are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce3+ to Ce4+), ionic potential, and complexation of Ce4+ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation.  相似文献   

9.
We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.  相似文献   

10.
Instrumental neutron activation analysis was used to determine nine rare earth elements (REE), Sc and five high field‐strength elements (HFSE) in the Multani Mitti (MM) clay. Chondrite‐normalised rare earth element patterns for the MM clay compared with those for the Post‐Archaean Australian Shale (PAAS), Upper Continental Crust (UCC) and North American Shale Composite (NASC) showed enrichment of light REEs and depletion of heavy REEs with a slight negative Eu anomaly. The Multani Mitti clay showed close resemblance to PAAS and NASC in its average REE and HFSE contents. Positive correlations between La/Ce, La/Sm, La/Yb, Zr/Hf, Th/U and Th/Ta ratios predict enrichment of LREEs, Zr and Th and depletion of HREEs. A parent source of felsic origin for the MM clay is also endorsed through the high La/Th and low Th/Sc ratios observed.  相似文献   

11.
贵州省松桃县道坨超大型锰矿床的发现及其成因探讨   总被引：5，自引：0，他引：5  
贵州省松桃县道坨锰矿床是新发现的一个超大型全隐伏锰碳酸盐矿床。文章阐述了该矿床的发现概况及基本的地质和地球化学特征,并应用锰矿石和含锰黑色页岩的元素和碳同位素地球化学特征对菱锰矿的形成机制提出了制约。道坨超大型锰矿床的发现是填图及对区域地质资料综合分析的结果。该矿床具有品位高、厚度大、呈层性好及展布广等特点。其锰矿石的主量元素特征为Al2O3、TiO2、Fe2O3含量较低,P2O5中等程度富集,MnO、MgO含量相对较高,Fe/Mn比值低。在微量元素方面,锰矿石显示出较为明显的Co富集,含锰黑色页岩则显示出较为明显的Co、Mo富集;在稀土元素方面,锰矿石具有较高的稀土元素总量,轻微的"帽式"稀土元素PAAS标准化配分模式及明显的Ce正异常,含锰黑色页岩的稀土元素总量与PAAS接近,其稀土元素PAAS标准化配分模式较为平坦,无Ce异常。碳同位素测试结果显示出菱锰矿富集碳的轻同位素,表明在菱锰矿形成过程中存在有机碳的参与。文章表明,道坨锰矿床内的锰是以氧化物或氢氧化物的形式沉淀,菱锰矿是在缺氧且富含有机物质的成岩环境中转化而成。  相似文献   

12.
Basaltoids of the Vendian–Cambrian Kulbyurstyug volcanic complex in the eastern part of Kuznetsk Alatau have a high content of titanium (TiO2 3–4 wt %). They are relatively enriched with LILE and HFSE (Ba 360–900, Zr 160–726, Nb 66–101, ΣREE up to 225–329 ppm), and demonstrate a fractionated spectrum of REEs (La/Yb ～ 13–17), high Nb/U (44–66), and low Th/Ta and Th/Nb. These features are comparable with derivatives of OIB (Ocean Island Basalts) magmatism. The rock geochemistry suggests the possible formation of an initial mafic melt in the garnet-bearing peridotite mantle with 2–4% degree of melting and the presence of a small amount of spinel. By the age and composition, the studied volcanics are correlated with the OIB magmatism products, occurring in the adjacent Gorny Altai and also considered to be derivatives of intraplate magmatism of Riphean–Early Cambrian age. This magmatism was caused by plume activity during formation of the Paleo-Asian Ocean.  相似文献   

13.
This work reports, for the first time, the mineralogical and geochemical characteristics of the Cretaceous sedimentary kaolin deposits in the Red Sea area, Egypt and sheds the light on their source. Mineralogical and geochemical analyses of both bulk deposits and the sand and clay fractions of these deposits indicated that they are composed of kaolinite (average of 75 wt.%) and quartz (average of 22 wt.%). Traces of anatase (average of 1 wt.%) were identified in all kaolin samples, while traces of halite (average of 2 wt.%) and hematite (average of 1 wt.%) were reported in the majority of the analyzed samples. The clay fractions show relatively high contents of TiO2 (average of 2.1%), Ni (average of 103 ppm), Nb (average of 98 ppm), Y (average of 67 ppm), and Zr (average of 630 ppm). Sum of the rare earth elements (ΣREE) in the clay fractions varies between 193 and 352 ppm. Chondrite-normalized REE patterns show enrichment of the light REE relative to the heavy REE ((La/Yb)N = 9) and negative Eu anomaly (Eu*/Eu = 0.67).  相似文献   

14.
The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r 2= 0.98) and Mn + Fe + Cu + Ni (r 2= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along with La(n)/Yb(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention of a bottom water REE pattern. An erratum to this article is available at .  相似文献   

15.
Rare earth element (REE) and strontium isotope data (87Sr/86Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The 87Sr/86Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.  相似文献   

16.
The Kalahari Manganese Deposit (KMD) is the largest land-based manganese deposit, hosting approximately 80% of the world's known, mineable manganese resources. The deposit, located near Kuruman in the Northern Cape Province of South Africa, is one of five erosional relics of the Paleoproterozoic (ca. 2.2 Ga) Hotazel Formation, with sedimentary manganese ores occurring as up to 50 m thick beds interbedded with banded iron-formation (BIF) and hematite lutite.The study focuses on the manganese ores of the Nchwaning–Gloria mining area of the northern KMD. In this area, pronounced mineralogical and major element alteration was imparted on the sedimentary manganese ores by a structurally-controlled hydrothermal fluid flow event. Most notable effects of hydrothermal alteration are the decomposition and leaching of Ca- and Mg-carbonate, and marked residual enrichment of manganese. On the basis of mineral assemblage, grade, texture and geochemical characteristics, three ore types were distinguished in the studied sample set, classified into least altered (LA), partially altered (PA) and advanced altered (AA) types. Advanced altered ores may be further classified into five different types, based on mineral assemblages that contain hausmannite and/or braunite as significant minerals. The rare earth element (REE) geochemistry of these fundamental ore types was studied in detail, to document REE mobility during hydrothermal alteration.Total REE concentrations in LA ores were found to be very low (14–22 ppm) and remarkably uniform, within the range typically observed for BIF. Hydrothermal alteration results in residual enrichment and a much larger scatter in REE contents. A small Ce anomaly observed in the protolith remains similar in magnitude when observed in PAAS-normalised REE plots. The data define, however, a power trend in the (Ce/Ce*) vs (Pr/Pr*) diagram. Such behaviour is interpreted in terms of a conservative system that was predominantly protolith-buffered. Local remobilisation of REE during hydrothermal alteration is attributed to the dissolution of diagenetic apatite and redistribution of hydrothermal trace minerals, including neoformed apatite, monazite and cerianite.  相似文献   

17.
The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe2O3, the studied iron ores show relatively high contents of SiO2 and Al2O3 due to the abundance of quartz and chamosite. P2O5 ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO2, Al2O3, and TiO2 suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P2O5 indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO2, and Al2O3 around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO2 and Al2O3, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.  相似文献   

18.
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.  相似文献   

19.
《Sedimentary Geology》2006,183(3-4):203-216
This paper presents rare earth element (REE) geochemistry of siliceous deposits from which hydrothermal activity and basin evolution are elucidated, in the Late Devonian, in the Yangshuo basin, South China, where siliceous deposits widely occurred as nodular chert in the deep-water limestones and bedded chert interbeded with tuffaceous chert in the early Late Devonian. Both nodular and bedded cherts are characterized by very low La abundances (avg. 2.07 and 2.49 ppm, respectively), intermediate negative Ce anomalies (Ce/Ce*: avg. 0. 69 and 0.61), slight to intermediate positive Eu anomalies (Eu/Eu*: avg. 1.33 and 1.57), and low to intermediate shale-normalized Lan/Ybn values (avg. 0.86 and 0.52) and intermediate Lan/Cen values (avg. 1.61 and 1.72). These suggest both nodular and bedded cherts formed in the open marine basin of South China, rather than in the intracontinental rift basin as previously assumed, with involvement both with seawaters as indicated by intermediate negative Ce anomalies and generally LREE-depleted patterns, and hydrothermal vent fluids as indicated by convex, less LREE-depleted patterns with apparent positive Eu anomalies. In comparison with nodular and bedded chert, the tuffaceous chert has the highest La abundances (avg. 17.11 ppm), similar ranges of Ce anomalies (avg. 0.63) and Lan/Cen values (avg. 1.77), but lower Lan/Ybn values (avg. 0.48) and no apparent positive Eu anomalies (avg. 0.97). This suggests that the tuffaceous fallouts were also significantly modified by the hydrothermal fluid and seawater. Rapid spatial variations of Eu/Eu* values and degree of LREE-depletions in the studied basin are recognized, characterizing a spatially differential hydothermal activity that is not well discriminated by major element features. Such a difference in hydrothermal activity is interpreted as having been related to the intensity and depth of syndepositional tectonic activity, reconciling the structural pattern unraveled by stratigraphic packages.  相似文献   

20.
The Sipingshan gold deposit, located in the eastern part of the Nadanhada Terrane, is hosted within cherts and silicified breccias of the Upper Cretaceous Sipingshan Formation and rhyolites of the Upper Cretaceous Datashanlinchang Formation. The orebodies are composed of gold- and pyrite-bearing cherts, silicified breccias, and quartz veins accompanied by various types of wall rock alteration, including silicification, pyritization, sericitization, chloritization, pyrophyllitization, and carbonatization. LA-ICP-MS U–Pb zircon ages determined for the ore-bearing rhyolites range between 122 ± 1.4 and 135.2 ± 1.9 million years slightly older than the metallogenic age of the Sipingshan gold deposit. The rhyolite has aluminium saturation index values ranging from 0.015 to 1.25 and shows the following features: enrichment in LILE (e.g. Rb, Pb, K, and Th); depletion of Ba, Sm, and Ti; and negative Eu anomalies. These geochemical characteristics indicate that (1) the rhyolite contains features typical of S-type granites; (2) the felsic magma likely originated through partial melting of the continental crust; and (3) plagioclase crystals were present in the partial melt residues in the magma source region, or else magma evolution involved plagioclase fractionation. The host cherts have high Al/(Al + Fe + Mn) ratios (0.23–0.81, averaging 0.60) and low Al2O3 and TiO2 contents. Their North American shale-normalized REE patterns are characterized by flat REE, slightly positive Eu anomalies, no Ce anomalies, and (La/Yb)SN ratios of 1.27–1.38, indicating that these cherts formed in a continental margin environment. In addition, the analysed cherts have low ΣREE (1.56–3.64 ppm) and Zr (9.1–13.5 ppm) contents, suggesting a hydrothermal origin. Fluid inclusions in quartz veins show elliptical to irregular shapes that range from 5 to 12 μm in size and have homogenization temperatures of 118.7–223.4°C, densities of 0.84–0.94 g/cm3, and pressures of 21.2–51.4 MPa, indicating that the hot-spring-type Sipingshan gold deposit is epithermal in origin.  相似文献   

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