Chemistry of Late Early Triassic Siliceous Claystone ('Toishi-type' Shale) from the Oritate Area, Sambosan Belt, Kyushu, Southwest Japan

Abstract. Inorganic chemical compositions are determined for late Early Triassic siliceous claystone ('Toishi-type' shale) and associated chert from Oritate area, Sambosan Belt, Kyushu, southwest Japan. The siliceous claystone is similar in chemical composition to Post-Archean Australian Shale (PAAS), but is depleted in Ca, Sr, Mn, and Fe and slightly enriched in Cu, Zn, P, and rare earth elements (REEs). The siliceous claystone and associated chert have flat REE patterns with positive Eu anomalies and no distinct Ce anomaly. The siliceous claystone and associated chert have largely constant Ti/Al, Th/Al, and Nb/Al ratios compared to the variable ratios found in siliceous shale and sandstone deposited close to land in a trench setting. This suggests that the claystone and chert were deposited in a deep-sea pelagic environment and were derived mainly from the suspended fraction, including eolian dust and material transported from distant lands, rather than from turbidity currents that occurred close to land. The low Ca contents of the analyzed rocks indicate deposition below the calcium-carbonate compensation depth. The depletion of Mn and Fe, and no distinct Ce anomaly in the Oritate siliceous claystone are also evident, being similar to those in samples from the Sasayama and Kinkazan sections in the Mino-Tanba Belt, where oceanic anoxia developed during the Late Permian to earliest Triassic. This might suggest that oceanic anoxia prevailed through to the late Early Triassic.     

Facies analysis of the Semanggol Formation,South Kedah,Malaysia: A possible Permian–Triassic boundary section

Although the Permian–Triassic Semanggol Formation is widely distributed in northwestern Peninsula Malaysia and is made of various lithofacies, its sedimentology and possible relation with the Permian–Triassic boundary (PTB) were not considered before. In this study, detailed facies analysis was conducted for two sections of the Semanggol Formation at the Bukit Kukus and Baling areas, South Kedah to clarify its sedimentology and relation to the PTB. Four facies from the Permian part of the Semanggol Formation that were identified at the Bukit Kukus section include laminated black mudstone, interbedded mudstone and sandstone, volcanogenic sediments, and bedded chert. In Baling area, the Triassic part of the formation is classified into three members. The lower member comprises of claystone and bedded chert facies, while the middle member is composed of sandstone and claystone interbeds (rhythmite). On the other hand, the upper member is grouped into two main units. The lower unit is mainly claystone and includes two facies: the varve-like laminated silt and clay and massive black claystone. The upper unit is composed of various sandstone lithofacies ranging from hummocky cross stratified (HCS) sandstone to thinly laminated sandstone to burrowed sandstone facies. The HCS sandstones occur as two units of fine-grained poorly sorted sandstone with clay lenses as flaser structure and are separated by a hard iron crust. They also show coarse grains of lag deposits at their bases. The laminated black mudstone at the lowermost part of the Semanggol Formation represents a reducing and quite conditions, which is most probably below the fairweather wave base in offshore environment that changed upwards into a fining upward sequence of tide environment. Abundance of chert beds in the volcanogenic sediments suggests the deposition of tuffs and volcanic ashes in deep marine setting which continues to form the Permian pelagic bedded chert and claystone. The bedded chert in the lower member of the Triassic section suggests its formation in deep marine conditions. The rhythmic sandstone and claystone interbeds of the middle member are suggestive for its formation as a distal fan of a turbidite sequence. Lithology and primary sedimentary structure of the upper member suggest its deposition in environments range from deep marine represented by the varve-like laminated silt and clay to subtidal environment corresponds to the massive black claystone to coastal environment represented by the hummocky sandstone units and reaches the maximum regression at the hiatus surface. Another cycle of transgression can be indicated from the second hummocky unit with transgressive lag deposits that develops to relatively deeper conditions as indicated from the formation of relatively thick laminated sandstone and bioturbated massive sandstone facies that represent tidal and subtidal environment, respectively. Late Permian lithological variation from the radiolarian chert into early Triassic claystone probably resulted from a decrease in productivity of radiolarians and might represent a PTB in the Semanggol Formation. Volcanogenic sediments in the studied section can be used as an evidence for volcanic activities at the end of the Permian, which is probably connected to the nearby volcanic ash layers in the eastern China, the ultimate cause of the PTB in this area. Black mudstone in the Permian part of the studied section may be interrelated to the Latest Permian Anoxia that started to build in the deep ocean well before the event on shallow shelves.     

A giant late Precambrian chert-bearing olistostrome discovered in the Bohemian Massif: A record of Ocean Plate Stratigraphy (OPS) disrupted by mass-wasting along an outer trench slope

An intriguing example of chert–graywacke olistostrome is exceptionally well preserved within the late Neoproterozoic to early Cambrian Blovice accretionary wedge, Bohemian Massif. The olistostrome exhibits a block-in-matrix fabric defined by chert blocks isolated within the graywacke matrix. The major and trace element composition indicates two distinct types of cherts that formed either in a hydrothermal pelagic or hemipelagic environment supplied with a distal terrigenous material. The former is documented by elevated contents of Fe, Co, Zn, Ni, and Ti whereas the latter by high Al₂O₃ contents, relatively lower La_N/Ce_N ratios, and higher Eu/Eu* and Ce/Ce* values. Based on these geochemical data integrated with field observations and detrital zircon U–Pb ages of the host graywackes (determined using laser ablation ICP-MS), a new model for the origin of chert–graywacke association is proposed. The cherts are interpreted as representing pelagic and hemipelagic members of the Ocean Plate Stratigraphy (OPS) that formed in a sedimentary basin, carried on top of a subducting plate towards the trench. While moving over the outer swell (rise), the chert basin was intensely fractured and disrupted into large blocks or slabs. Subsequent motion of the plate brought the blocks onto an outer trench slope where they became gravitationally unstable to slide down and mix in the trench with distal, ca. 580–570 Ma turbidites derived from the overriding plate. Finally, this chert–graywacke olistostrome was covered by younger, ca. 560–547 Ma trench-fill turbidites (devoid of chert blocks) and accreted to the accretionary wedge toe, deformed, buried, and exhumed back to the wedge surface. We propose that such an olistostrome composed of pelagic/hemipelagic chert blocks and terrigenous, arc-derived graywacke matrix represents a rarely documented case of submarine, outer trench slope mass-wasting deposits and may be considered a new type of subduction-related mélanges. We coin the term outer-trench-slope mélange.     

Rare Earth, Major and Trace Elements in the Kunimiyama Ferromanganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Rare earth, major and trace element geochemistry is reported for the Kunimiyama stratiform ferromanganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The deposit immediately overlies greenstones of mid-ocean ridge basalt (MORB) origin and underlies red chert. The ferromanganese ores exhibit remarkable enrichments in Fe, Mn, P, V, Co, Ni, Zn, Y and rare earth elements (excepting Ce) relative to continental crustal abundance. These enriched elements/ Fe ratios and Post-Archean Average Australian Shale-normalized REE patterns of the ferromanganese ores are generally analogous to those of modern hydrothermal ferromanganese plume fall-out precipitates deposited on MOR flanks. However in more detail, Mn and Ti enrichments in the ferromanganese ores are more striking than the modern counterpart, suggesting a significant contribution of hydrogenetic component in the Kunimiyama ores. Our results are consistent with the interpretation that the Kunimiyama ores were umber deposits that primarily formed by hydrothermal plume fall-out precipitation in the Panthalassa Ocean during the Early Permian and then accreted onto the proto-Japanese island arc during the Middle Jurassic. The presence of strong negative Ce anomaly in the Kunimiyama ores may indicate that the Early Permian Panthalassa seawater had a more striking negative Ce anomaly due to a more oxidizing oceanic condition than today.     

Provenance and distribution of tethyan pelagic and hemipelagic siliceous sediments,pindos mountains,Greece

The broad range of time over which ribbon bedded cherts were deposited does not extend into the present marine environment, and no ribbon cherts have been recovered from the sea floor by the Deep Sea Drilling Project. The depositional environment of bedded cherts is difficult to determine, but extra-silicic impurities in the rock may offer clues about the provenance of the non-biogenic component. To test the usefulness of relative abundances of the extra silicic components in extracting information on the depositional environment of the chert, I analyzed the major element chemistry of chert samples from a broad range of environments including ophiolite-associated chert from the Franciscan Formation of California, deep-sea chert and porcellanite from the northwest Pacific (DSDP Leg 32), shallow pelagic shelf chert nodules from the Chalk of Britain, continental marginal basin chert from the Monterey Formation of California, and continental marginal basin chert from the Pindos Zone of Greece. The ratios FeO/A1₂O₃, TiO₂/A1₂O₃ and A1/A1+Fe+Mn were considered in detail. The interpretative logic is simple but empirically supported by observations of these ratio values at different depositional environments in the Pacific: A1 is concentrated most highly in continental material while Fe and Mn are more concentrated in pelagic sediments. FeO/A1₂O₃ can be used to differentiate between ophiolite associated chert and chert associated only with other sediments. TiO₂/A1₂O₃ is not a useful indicator, possibly because of the equalizing effect of widespread eolian transport. The A1/A1+Fe+Mn ratio was measured in detail in one stratigraphic section in central continental Greece. This ratio varied with the type of sediment admixture, decreasing in value after the influx of ophiolite debris-bearing sediments, even when their presence was undetectable in hand sample or under petrographic microscope.To help clarify the paleogeography of the main study area, the Pindos Zone, and to identify sources and dispersal patterns of extra-basinal materials, isopach maps of sedimentary facies of the Pindos were constructed. Superimposed directly upon the series of imbricated thrust slices that comprise the Pindos Zone, the maps are at best compressed pictures of the Pindos Sea Floor. Persistent regional variation of facies thicknesses over time suggests the existence of several smaller depressions surrounded by submarine highs in the Pindos Basin.     

A specific Ce oxidation process during sorption of rare earth elements on biogenic Mn oxide produced by Acremonium sp. strain KR21-2

Sorption of rare earth elements (REEs) and Ce oxidation on natural and synthetic Mn oxides have been investigated by many researchers. Although Mn(II)-oxidizing microorganisms are thought to play an important role in the formation of Mn oxides in most natural environments, Ce oxidation by biogenic Mn oxide and the relevance of microorganisms to the Ce oxidation process have not been well understood. Therefore, in this study, we conducted sorption experiments of REEs on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. The distribution coefficients, K_d(REE), between biogenic Mn oxide (plus hyphae) and 10 mmol/L NaCl solution showed a large positive Ce anomaly and convex tetrad effect variations at pH 3.8, which was consistent with previous works using synthetic Mn oxide. The positive Ce anomaly was caused by oxidation of Ce(III) to Ce(IV) by the biogenic Mn oxide, which was confirmed by analysis of the Ce L_III-edge XANES spectra. With increasing pH, the positive Ce anomaly and convex tetrad effects became less pronounced. Furthermore, negative Ce anomalies were observed at a pH of more than 6.5, suggesting that Ce(IV) was stabilized in the solution (<0.2 μm) phase, although Ce(III) oxidation to Ce(IV) on the biogenic Mn oxide was confirmed by XANES analysis. It was demonstrated that no Ce(III) oxidation occurred during sorption on the hyphae of strain KR21-2 by the K_d(REE) patterns and XANES analysis. The analysis of size exclusion HPLC-ICP-MS showed that some fractions of REEs in the filtrates (<0.2 μm) after sorption experiments were bound to organic molecules (40 and <670 kDa fractions), which were possibly released from hyphae. A line of our data indicates that the negative Ce anomalies under circumneutral pH conditions arose from Ce(III) oxidation on the biogenic Mn oxide and subsequent complexation of Ce(IV) with organic ligands. The suppression of tetrad effects is also explained by the complexation of REEs with organic ligands. The results of this study demonstrate that the coexistence of the biogenic Mn oxide and hyphae of strain KR21-2 produces a specific redox chemistry which cannot be explained by inorganic species.     

Geochemistry and Origin of Ananai Stratiform Manganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Major and trace element contents are reported for Permian manganese ore and associated greenstone from the Ananai manganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The manganese deposit occurs between greenstone and red chert, or among red chert beds. Chemical compositions of manganese ore are characterized by enrichments in Mn, Ca, P, Co, Ni, Zn, Sr and Ba, and negative Ce and positive Eu anomalies relative to post-Archean average Australian Shale (PAAS). Geochemical features of the manganese ore are similar to those of modern submarine hydrother-mal manganese deposits from volcanic arc or hotspot setting. In addition, geochemical characteristics of the greenstone closely associated with the Ananai manganese deposit are analogous to those of with-in plate alkaline basalt (WPA). Consequently, the Ananai manganese deposit was most likely formed by hydrothermal activity related to hotspot volcanism in the Panthalassa Ocean during the Middle Permian. This is the first report documenting the terrestrially-exposed manganese deposit that was a submarine precipitate at hotspot.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

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.     

Implications of elemental concentrations for provenance, redox conditions, and metamorphic studies of shales and limestones near Pueblo, CO, USA

Major element and some trace element compositions (including the REE) of shales, carbonate-rich shales, and limestones of Late Cretaceous age have been analyzed at two outcrops near Pueblo, CO. Elemental ratios that are characteristic of the provenance of terrigenous debris that are the least variable with changing percent acid insoluble residue vs. percent calcite are Th/Cr, La/Co, (La/Lu)_cn, and Eu/Eu*. The Ce/Ce*, La/Sc, and La/Cr ratios, however, are only constant when greater than 30% of a sample is composed of acid insoluble residue. At less than 30% acid insoluble residue, these elemental ratios increase markedly. The Th/Co and Th/Sc ratios are fairly constant from nearly 0% to about 60% acid-insoluble residue. Above 60% residue, these ratios increase due to the high concentration of Th in the Graneros to Hartland shales at Everhart Ranch. The average of the Th/Co, Th/Sc, Th/Cr, La/Co, La/Sc, and La/Cr ratios are similar to those of the MCS (mid-continent shales) and PAAS (Post-Archean Australian shales). Thus, these carbonate-rich to carbonate poor rocks analyzed in this study contain terrigenous debris that has been derived from granitoids similar to those that supplied debris to the MCS and PAAS. The Ce/Ce* ratios are lower and the Mn* (Mn*=log[(Mn_sample/Mn_shales)/(Fe_sample/Fe_shales)]) values are more positive in the more calcite-rich Bridge Creek and Ft. Hays limestones than in the other units, suggesting that they formed in an oxidizing environment. The Ce/Ce* are the highest and the Mn* values are the most negative in the Graneros to Hartland shales, suggesting that they formed under more reducing conditions.The elemental concentration of one sample relative to that of another sample over a few meters distance usually vary in small amounts (e.g., medians of the ratios of the same elements between adjacent samples ranges from 1.06 to 1.70). However, the ratio of elemental concentrations between adjacent samples can sometimes be quite large. The least variation of elemental ratios between adjacent samples often occurs within the more carbonate-poor shales; the greatest variation occurs within the limestones. Thus, trying to decipher local movement of elements due to metamorphism in similar carbonate shale-limestone sequences should be done cautiously since local elemental variation due to sedimentary processes can be large.     

湖北黄石二门二叠系/三叠系界线剖面长兴阶牙形刺分带及有机碳同位素的变化

湖北黄石二门二叠系/三叠系界线剖面出露完好,原始沉积连续,由乐平统龙潭组保安段灰黑色硅质岩、大隆组黑色硅质岩—硅质泥岩和下三叠统大冶组黑灰色泥岩以及泥岩夹灰岩组成,为介于典型浅水碳酸盐岩型与深海硅质岩型二叠系/三叠系界线剖面之间的半深海剖面。长兴阶可划分为Clarkinasubcarinata—Clarkinawangi及Clarkinachangxingensis两个牙形刺带。后者又可划分为3个亚带,自下而上依次为Clarkinachangxingensischangxingensis—Clarkinadeflecta亚带、Clarkinameishanensis亚带及Waning—Clarkina亚带,完全可以与二叠系/三叠系界线的全球层型剖面与点进行对比。另外,二叠纪末牙形刺的生态演化呈阶段性绝灭模式;有机碳同位素值在二叠纪/三叠系界线处出现明显的负偏移,指示了二叠纪/三叠纪之交生物绝灭后海水表层水原始产率的降低以及大气和海水中CO2含量的增加。     

泰国北部难河构造带二叠纪放射虫、硅质岩和玄武岩

在泰国北部难河构造带Pha Som变质杂岩中发现保存很好的放射虫硅质岩、玄武岩地层层序.层状硅质岩含放射虫化石Follicucullus porrectus, 地质时代为中二叠世晚期至晚二叠世早期.其硅质岩SiO₂含量均在92.5%以上, Al/ (Al+Fe+Mn) 平均比值为0.51, Ce/Ce*比值为1.14, 为大陆边缘型硅质岩.玄武岩具有富集大离子亲石元素与高场强元素以及轻稀土富集等洋岛玄武岩的特点.说明难河构造带中-晚二叠世之交存在洋岛型火山岩和靠近大陆边缘的深海盆地硅质岩, 代表了小洋盆的沉积组合.该构造带闭合时间应在晚二叠世与晚三叠世之间.      

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau,East Sea

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.     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

Genesis for Rare Earth Elements Enrichment in the Permian Manganese Deposits in Zunyi,Guizhou Province,SW China

The Zunyi manganese deposits, which formed during the Middle to Late Permian period and are located in northern Guizhou and adjacent areas, are the core area of a series of large-medium scale manganese enrichment minerogenesis in the southern margin and interior of the Yangtze platform, Southern China. This study reports the universal enrichment of rare earth elements(REEs) in Zunyi manganese deposits and examines the enrichment characteristics, metallogenic environment and genesis of REEs. The manganese ore bodies present stratiform or stratoid in shape, hosted in the silicon–mud–limestones of the Late Permian Maokou Formation. The manganese ores generally present lamellar, massive, banded and brecciated structures, and mainly consist of rhodochrosite, ropperite, tetalite, capillitite, as well as contains paragenetic gangue minerals including pyrite, chalcopyrite, rutile, barite, tuffaceous clay rock, etc. The manganese ores have higher ΣREE contents range from 158 to 1138.9 ppm(average 509.54 ppm). In addition, the ΣREE contents of tuffaceous clay rock in ore beds vary from 1032.2 to 1824.5 ppm(average 1396.42 ppm). The REEs from manganese deposits are characterized by La, Ce, Nd and Y enriched, and existing in the form of independent minerals(e.g., monazite and xenotime), indicating Zunyi manganese deposits enriched in light rare earth elements(LREE). The Ce_(anom) ratios(average-0.13) and lithofacies and paleogeography characteristics indicate that Zunyi manganese deposits were formed in a weak oxidation-reduction environment. The(La/Yb)_(ch), Y/Ho,(La/Nd)_N,(Dy/Yb)_N, Ce/Ce* and Eu/Eu* values of samples from the Zunyi manganese deposits are 5.53–56.92, 18–39, 1.42–3.15, 0.55–2.20, 0.21–1.76 and 0.48–0.86, respectively, indicating a hydrothermal origin for the manganese mineralization and REEs enrichment. The δ~(13) C_(V-PDB)(-0.54 to-18.1‰) and δ~(18) O_(SMOW)(21.6 to 26.0‰) characteristics of manganese ores reveal a mixed source of magmatic and organic matter. Moreover, the manganese ore, tuffaceous clay rock and Emeishan basalt have extremely similar REE fractionation characteristic, suggesting REEs enrichment and manganese mineralization have been mainly origin from hydrothermal fluids.     

Distribution of Rare Earth Elements in Early Permian Reef-Island Ocean Sediments in Eastern Kunlun

Based on the study of stratigraphy and fossils, the Early Permian ocean in eastern Kunlun is recognized as a kind of reef-island ocean, in which there exist many different kinds of sediment, including patch carbonate platform, reef fades, transitional facies and deep basin sediments. It has been found that the total contents of REEs increase gradually from carbonate platform facies to deep basin facies. Meanwhile, sediments of different facies have different REE distribution patterns and different Ce anomalies. Most of the sediments of patch carbonate platform facies or reef facies are characterized by extremely negative Ce anomalies or moderately negative Ce anomalies (Ce/Ce*=0.33 to 0.55), and medium or thin-bedded limestones of transitional facies by moderately negative Ce anomalies (Ce/Ce*=0.49 to 0.60). However, sediments of deep basin facies show weak or no negative Ce anomalies (Ce/Ce*=0.69 to 1.47), among which the value of Ce/Ce* in the radiolarian chert is 1.47.     

鄂西地区上二叠乐平统大隆组硅质岩成因及有机质富集机理

晚二叠世是古生代环境、生物演化的关键时期,发育广泛的富有机质沉积,并成为南方重要的烃源岩层位。为了解该时期的富有机质堆积机理,我们选择了鄂西台内盆地晚二叠世大隆组富有机质硅质岩(TOC平均值为5.8%,峰值为18%)作为研究对象。硅质岩中常量元素Al/Fe均值为0.79,Mn/Ti均值为0.21,显示为大陆边缘环境下的生物成因,即非热水成因。∑REE值与Al2O3含量有着良好的正相关关系,表明当时陆源物质的输入对硅质岩的形成有很大影响。微量元素U/Th、V/(V+Ni)均说明硅质岩沉积环境为缺氧水体环境。通过对草莓状黄铁矿粒径的统计表明,大多数(64%～89%)的草莓状黄铁矿粒径小于5μm,反映缺氧甚至硫化的环境。而且,U、V、Mo的富集以及Ni、Cu元素的亏损说明水体的缺氧主要是由于海水分层,水体循环受阻造成的。TOC与氧化还原参数的变化步调基本一致,两者有着较好的正相关关系,而与生产力指标Ba/Al相关性很差,说明有机质富集主要是由水体的缺氧而不是初级生产力控制的。     

Characteristics of Rare Earth and Trace Element Patterns in Bedded Cherts from the Bottom of the Lower Cambrian in the Northern Tarim Basin, Northwest China and Their Genetic Significance

The sedimentary sequence of the Lower Cambrian is a key interval to reveal the early evolution history of the Earth and there occur widespread cherts worldwide. These cherts possibly carry important information to decipher the breakup process of the Rodinia Continent. Black rock series at the bottom of the Lower Cambrian in the Northern Tarim Basin, China, is composed of black shales interbedded with thin-bedded cherts. Ten chert samples were systematically collected from two outcrops at Xiaoerbulak and Sogatbulak, 8.8 and 7.5 m thick respectively. The cherts were crushed, and were analyzed for trace element and rare earth concentrations. Trace elements such as V, Cu, Zn, U, Pb, Ba, Cd, Ag, Mo,As and Sb are highly enriched, and others such as Rb, Zr, Cs, Hf, Ta, W, T1, Bi and Th are highly depleted in the cherts.These trace element patterns suggest that the cherts may be of deep crustal origin. The low ratios of Th/U and Rb/Sr further suggest that the cherts are of earth interior sources or received hydrothermal input during their deposition. Chondritenormalized Eu/Eu* value markedly decreases upward in the section from 5.54 at the lowermost to 0.73 at the top, and NASC-normalized Eu/Eu* value decreases from 8.05 to 1.03. The relatively high Eu/Eu* ratio for the cherts from the northern Tarim Basin is most likely due to a hydrothermal input (e.g., Eu/Eu*-10). The systematic decrease of Eu/Eu* ratio from the bottom to the top of the section reflects that the hydrothermal input is the largest in the lowermost portion of the section and gradually decreases upward. The chondrite-normalized Ce/Ce* ratio ranges from 0.42 to 0.83, with an average of 0.60. North American Shale Composite (NASC)-normalized Ce/Ce* ratio ranges from 0.42 to 0.79, with an average of 0.57. Negative Ce anomalies are distinct. EREEs in the cherts generally increase from 10.50 ppm at the bottom to 35.97 ppm at the top of the sampled section. NASC-normalized (La/Lu)N ratio decreases from 2.72 at the bottom to 0.67 at the top. NASC-normalized (La/Ce)N ratio increases from 1.36 at the bottom to 3.13 at the top. These REE patterns are very similar to those for the cherts deposited in the pelagic ocean-basin floor in the Franciscan Complex exposed at Marin Headlands, California (F-MH chert) (Murray et al., 1991). These geochemical signatures are inconsistent with our previous sedimentological data, which suggests a continental shelf setting. Based on multiple lines of evidence including high TOC content in the concomitant black shales, phosphorite at the bottom of black rock series, regional rise of sea level,and beginning of the southern Tianshan Ocean geotectonic cycle, the authors infer that the hydrothermal fluid was carried to the continental shelf by upwelling from a divergent pelagic ocean floor setting.     

广西那坡裂陷盆地晚古生代硅质岩地球化学特征及其地质意义

广西那坡裂陷盆地位于右江盆地南缘,晚古生代该盆地广泛分布包括硅质岩、泥岩和海相玄武岩在内的深水相沉积.对盆地内上泥盆统榴江组和中下二叠统四大寨组硅质岩地球化学特征研究表明,硅质岩SiO₂含量为88.55%~99.03%,PAAS组成含量小于20%,指示其含有较低的陆源碎屑组成.硅质岩的Al/(Al+Fe+Mn)值为0.45~0.94,Eu/Eu*值为0.51~0.95,为非热液成因硅质岩.除去SiO₂稀释作用的影响后,硅质岩具有较高的稀土元素含量(∑REE+Y含量相当于PAAS组成的2~5倍),指示其形成于相对远离陆源供应的环境.岩信和鱼塘上泥盆统榴江组硅质岩具有中等的Ce负异常(Ce/Ce*值分别为0.37~0.72和0.58~0.89)以及较明显的Y正异常(Y/Ho值分别为39.05~83.74和34.33~36.70),形成于远离陆源的开阔裂谷盆地环境.鱼塘中下二叠统四大寨组硅质岩具有明显的Ce负异常(Ce/Ce*值为0.12~0.33),显示成熟洋盆的地球化学特征.结合右江其他地区硅质岩的地球化学特征认为,晚古生代硅质岩的地球化学特征记录了右江盆地从晚泥盆世裂谷盆地到早中二叠世扩张为开阔洋盆的过程.      

淮北煤田二叠纪煤中稀土元素地球化学研究

从淮北煤田二叠系10,7,5,4和3煤层中采集34个样品,采用等离子体质谱（ICP-MS）、中子活化（INNA）、等离子体发射光谱（ICP-AES）等方法对样品中主量元素和稀土元素进行了测试,利用X射线衍射等方法对煤中矿物质及其煤质参数进行了测定。在各种测试的基础上,全面分析了稀土元素含量特征、空间分布规律、地球化学参数和分布模式,探讨了淮北煤田二叠纪煤中稀土元素的主要来源及其在煤中的主要赋存方式。研究表明：与华北和国内外其他地区相比,本区煤层中稀土元素相对富集;产于石盒子组煤中的稀土元素含量高于山两组的,在同一煤层中自下而下稀土元素含量有增高趋势,在顶底板中可能出现富集。Ce呈正异常,Eu明显负异常,不同煤层稀土元素的分布模式相似,稀土元素和灰分具有较好的正相关,∑REE与灰分、灰分中的主要元素以及典型陆源灰分中的微量元素正相关,与反映海相的低灰组分相关性较差。结合煤中矿物质的X射线衍射结果,分析获知,淮北煤田二叠纪成煤环境基本不受海水影响,稀土元素主要由陆源供给,而且主要赋存在以高岭石、伊利石为主的粘土矿物中。