The geochemistry of platinum group elements in marine oil shale—A case study from the Bilong Co oil shale,northern Tibet,China

The Bilong Co oil shale zone is located in the South Qiangtang depression. This zone, together with the Shengli River-Changshe Mountain oil shale zone in the North Qiangtang depression, northern Tibet plateau, represents the potentially largest marine oil shale resource in China. Seventeen samples including oil shale and micritic limestone were collected from the Bilong Co oil shale area to determine the concentrations, distribution patterns, occurrences and origins of platinum group elements (PGEs) in marine oil shale. The oil shale samples from the Bilong Co area exhibit very low total PGE contents ranging from 1.04 to 2.96 ng/g with a weighted mean value of 1.686 ng/g, while the micritic limestone samples from the Bilong Co area exhibit a little lower PGE value ranging from 0.413 to 1.11 ng/g. PGEs in oil shale samples are characterized by high contents in Pd (average 0.79 ng/g), Os (average 0.123 ng/g) and Pt (average 0.644 ng/g) compared with Ru (average 0.068 ng/g), Rh (average 0.033 ng/g) and Ir (average 0.026 ng/g). The highest values for individual PGEs are not uniformly distributed in the section. Clearly, the PGEs are generally enriched in the oil shale samples near the boundary between micritic limestone and oil shale.The individual PGEs in oil shale samples from the Bilong Co area exhibit various modes of occurrence. Ruthenium and Pt occur mainly in pyrite, while Pd is associated mainly with organic matter and Mg-minerals. Rhodium and Os are controlled mainly by pyrite and organic matter. Iridium is present mainly in other Fe-bearing minerals, rather than pyrite. The PGEs in the Bilong Co oil shale are mainly of seawater origin and possibly influenced by terrigenous supply.     

藏北羌塘盆地胜利河油页岩干酪根特征及碳同位素指示意义

胜利河油页岩位于北羌塘盆地南部, 走向长超过34 km, 宽9 km。笔者对该油页岩各岩系干酪根进行了分离、镜鉴、元素分析和碳同位素分析, 结果表明, 该油页岩干酪根为Ⅱ型干酪根, 油页岩中干酪根含量较高, 介于15.79%~20.37%, 具有富氢少氧的特征, 其H/C和O/C比率分别为1.11~1.19和0.08~0.25, 为胜利河地区非常好的烃源岩。油页岩层干酪根13C相对富集, 具有相对较高的δ13CPDB值(-20.79‰~ -21.78‰), 与胜利河地区油页岩母源为较单一的藻类有关。藻类的大量繁殖造成了该类生物死亡埋藏速率远大于氧化速率, 在还原环境下大部分藻类还未被氧化就被埋藏, 从而保留了原始藻类略富13C的特征。胜利河油页岩的空间展布以及规模明显受古泻湖环境的控制。     

Characterization of the Lebanese Jurassic–Cretaceous carbonate stratigraphic sequence: a geochemical approach

The Lebanese crustal segment is part of a much larger carbonate platform deposited along the northwestern margin of the Arabian Plate, in the eastern Mediterranean region. It is made up mainly of Jurassic–Cretaceous carbonate rocks. Most of this stratigraphic sequence is exposed in the Nahr Ibrahim canyon and surrounding areas in central Lebanon. The various formations, from the oldest unit (the Lower Jurassic Kesrouane Formation) to the Upper Cretaceous Chekka Formation, are made up of different types of carbonate rocks including micritic limestone, medium‐ to coarse‐grained dolostone, biomicritic (chalk), biosparrudite limestone, micritic dolostone, pelmicrite, marl and marly limestone. Results of this first chemical investigation on the Lebanese carbonate platform show that the micritic limestone of the Kesrouane Formation is relatively enriched in Ca, Na and Sc, and has low rare‐earth element (REE) contents. The marl units of the Hammana Formation are enriched in Al, Fe, K, Ti, Rb, Ga, Nb, U, Th and REE. The chalk of the Chekka Formation shows the highest phosphorus content. A significant increase in P and Sr contents with time (from the Lower Jurassic to the Upper Cretaceous carbonate units) characterizes the Lebanese sequence; this is interpreted to be related to a possible increase in continental weathering rates during the Mesozoic. Enrichment in Ni, Ti and Nb in some formations is interpreted to be linked to Mesozoic volcanism in central Lebanon. The Cretaceous formations are subdivided according to their REE patterns into two distinct groups: limestones (Mdairej, Sannine and Maameltain formations) which are depleted in REE; and marl/chalk (Hammana and Chekka formations) which are significantly enriched in REE. On several geochemical variation diagrams, such as the K–Ti–P triangular plot, the Lebanese Mesozoic carbonate formations are found to occupy distinct compositional fields. Thus, carbonate geochemistry could prove to be a powerful tool (especially when combined with petrographic data) in characterizing and correlating carbonate formations (chemical stratigraphy), particularly in regions where field evidence may be limited. Results of this study have significant implications for the entire carbonate platform that covers a large part of the eastern Mediterranean region. Copyright © 2002 John Wiley & Sons, Ltd.     

Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA

Porewater (i.e., groundwater) samples were collected from multi-level piezometers across the freshwater-saltwater seepage face within the Indian River Lagoon subterranean estuary along Florida’s (USA) Atlantic coast for analysis of the rare earth elements (REE). Surface water samples for REE analysis were also collected from the water column of the Indian River Lagoon as well as two local rivers (Eau Gallie River, Crane Creek) that flow into the lagoon within the study area. Concentrations of REEs in porewaters from the subterranean estuary are 10-100 times higher than typical seawater values (e.g., Nd ranges from 217 to 2409 pmol kg⁻¹), with submarine groundwater discharge (SGD) at the freshwater-saltwater seepage face exhibiting the highest REE concentrations. The elevated REE concentrations for SGD at the seepage face are too high to be the result of simple, binary mixing between a seawater end-member and local terrestrial SGD. Instead, the high REE concentrations indicate that geochemical reactions occurring within the subterranean estuary contribute substantially to the REE cycle. A simple mass balance model is used to investigate the cycling of REEs in the Indian River Lagoon and its underlying subterranean estuary. Mass balance modeling reveals that the Indian River Lagoon is approximately at steady-state with respect to the REE fluxes into and out of the lagoon. However, the subterranean estuary is not at steady-state with respect to the REE fluxes. Specifically, the model suggests that the SGD Nd flux, for example, exported from the subterranean estuary to the overlying lagoon waters exceeds the combined input to the subterranean estuary from terrestrial SGD and recirculating marine SGD by, on average, ∼100 mmol day⁻¹. The mass balance model also reveals that the subterranean estuary is a net source of light REEs (LREE) and middle REEs (MREE) to the overlying lagoon waters, but acts as a sink for the heavy REEs (HREE). Geochemical modeling and statistical analysis further suggests that this fractionation occurs, in part, due to the coupling between REE cycling and iron redox cycling within the Indian River Lagoon subterranean estuary. The net SGD flux of Nd to the Indian River Lagoon is ∼7-fold larger than the local effective river flux to these coastal waters. This previously unrecognized source of Nd to the coastal ocean could conceivably be important to the global oceanic Nd budget, and help to resolve the oceanic “Nd paradox” by accounting for a substantial fraction of the hypothesized missing Nd flux to the ocean.     

云南乌蒙山区中下三叠统层序地层与沉积相研究——以彝良地区为例

通过对云南乌蒙山区彝良地区中下三叠统6条野外地质剖面测量及500余片岩石薄片镜下观察,结合区域构造特征,将该地区中下三叠统划分为6个三级层序。岩石类型主要为泥铁质粉砂岩、细粒长石岩屑砂岩、含钙质泥质粉砂岩、细粒岩屑砂岩、钙质胶结细粒岩屑砂岩、含生物屑泥晶灰岩、泥灰岩、泥灰岩-含海绿石铁质生物屑亮晶砂屑灰岩、微晶灰岩-泥晶灰岩-含海绿石泥晶砂屑灰岩、亮晶鲕粒灰岩、含粉砂质泥质微晶灰岩、微晶灰岩等。结合沉积物的结构特征、组分及其组合特征,认为彝良地区中下三叠统的沉积相主要为海岸和碳酸盐岩开阔台地相。     

Rare earth element sources and modification in the Lower Kittanning coal bed, Pennsylvania: implications for the origin of coal mineral matter and rare earth element exposure in underground mines

In this study, we examine the variations in rare earth elements (REE) from the Lower Kittanning coal bed of eastern Ohio and western Pennsylvania, USA, in an attempt to understand the factors that control mineral matter deposition and modification in coal, and to evaluate possible REE mixed exposure hazards facing underground mine workers. The results of this study suggest that the Lower Kittanning coal mineral matter is derived primarily from a clastic source similar to that of the shale overburden. While highly charged cations like silicon, aluminum, and titanium remained relatively immobile within the coal mineral matter, iron (primarily as pyrite) was added from nonclastic sources, either during deposition of the coal mire vegetation or subsequent to burial. Other mobile cations (e.g., alkali and alkaline earth elements) appear to have been added to and/or leached from the originally deposited clastic mineral matter. Most of the sulfur in the Lower Kittanning coal bed is bound as FeS₂ in the mineral matter, but a majority of samples contain a small excess of S that is most likely organically bound.In general, the total rare earth element content (TREE) in coal ash is greater than that in the shale overburden. If the primary source of mineral matter is the same as that for the overlying shale, then REE must have been enriched in the coal mineral matter subsequent to deposition. The total rare earth element content of Lower Kittanning coals correlates strongly with Si concentration ([TREE]≈0.0024 [Si]), which provides a threshold for evaluating possible mixed exposure health effects. Chondrite-normalized REE patterns reveal a shale-like light rare earth element (LREE) enrichment for the coal, similar to that of the shale overburden, again suggesting a primarily clastic REE source. However, when normalized to the shale overburden, most of the coal ash samples display a small but distinct heavy rare earth element (HREE) enrichment. We surmise that the HREE were added and/or preferentially retained during epigenesis, possibly associated with groundwater flow through the coal unit, but not necessarily in close association with the addition of iron. At least some of the “excess” HREE could be organically bound within the Lower Kittanning coal.     

Trace elements and their behaviour during the combustion of marine oil shale from Changliang Mountain, northern Tibet, China

The Shengli River–Changshe Mountain oil shale zone represents a potentially large marine oil shale resource in China. With the aim of better understanding the geochemistry of trace elements in marine oil shale and its combustion residues, 40 raw samples, 27 oil shale combustion residues and 29 selected minerals from Changliang Mountain oil shale are studied for geochemical analyses. The contents of Se, Cd, Mo, As, Cs, Pb, Sr and U in the oil shale samples are enriched from 1.47 to 33.91 times as compared with the Clarke values, whereas the concentrations of other elements are slightly higher/lower than the respective worldwide means. The most enriched elements in oil shale combustion residues are Se, Cd, Mo, As and U with enrichment values from 4.78 to 50.92. Trace elements with high volatile behaviour such as As, Co, Ni, Sc, Sn and V occur predominantly in organic matter and/or sulphides. Other non-volatile or slightly volatile trace elements (e.g., Be, Bi, Cs, Cu, Ga, Hf, Li, Nb, Rb, Ta, Th, W, Zr and REEs) may occur mainly in original and relatively refractory minerals in raw oil shale. The potentially hazardous trace elements in Changliang Mountain oil shale include As, Cd, Mo and Se. Arsenic and Se are controlled mainly by Fe-bearing minerals (probably pyrite) in Changliang Mountain oil shale. Cadmium is present mainly in dolomite, while Mo occurs mainly in organic matter.     

吉林省桦甸油页岩中稀土元素和微量元素的研究

对桦甸油页岩及其灰渣的矿物成分、主量元素、稀土元素和微量元素含量进行测定。结果表明：油页岩中稀土元素含量低于北美页岩(NASC)中的平均含量,REE球粒陨石标准化的分布模式曲线表现为负斜率,(La/Yb)_N的平均值大于1,属于轻稀土富集型;REE北美页岩标准化的分布模式曲线较平缓,（La/Yb）_S的平均值接近于1,轻重稀土分馏不明显。与球粒陨石和北美页岩相比,Eu有较严重的正异常。油页岩中的微量元素与北美页岩和地壳的平均值相比较,Sb、Nb、Cs、Zn、Bi、W等元素具有较高的富集度。油页岩灰渣中稀土元素和微量元素富集度均高于油页岩。     

Sources of rare earth elements in Appin Group limestones,Dalradian, north-east Scotland

Summary Rare earth elements (REE) have been determined in 15 samples from three metamorphosed limestone units of the Appin Group of the Dalradian of north-east Scotland. Total REE contents range from about 7 to about 50 ppm and the light REEs are slightly enriched compared with REE in the North American Shale Composite (NASC). In the more impure limestones, the dominant control on REE content was the clay mineral content in siliciclastic impurities derived from terrestrial sources. In the purer limestones, the correlation between REEs and iron is consistent with the well-documented relationship between iron and REEs in the aqueous environment. REE associated with terrestrial, iron-rich, flocculated organic colloids or marine, authigenic iron-manganese coats may well have contributed significantly to the REE contents. Weak Ce anomalies on NASC-normalised, REE variation diagrams in two samples with very low REE contents suggest a marine influence on the REE distribution.

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Die Quelle von Seltenen Erden in Kalken der Appin Gruppe, Dalradians, NE Schottland

Zusammenfassung An 15 Proben aus metamorphen Kalken der Appin Gruppe der Dalradians NE Schottlands wurde die Zusammensetzung der Seltenen Erden (REE) bestimmt. Der Gesamtgehalt an REE variiert von 7 bis 50 ppm, wobei die leichten REE im Vergleich zum North American Shale Composite (NASC) leicht angereichert sind. In unreinen Kalken wird der REE-Gehalt vom Tonmineralanteil der silikatisch-klastischen Verunreinigungen, die einer terrestrischen Quelle entstammen, kontrolliert. In reinen Karbonatgesteinen besteht eine Korrelation zwischen den REE und Fe, eine Beziehung, die für ein wässriges Milieu bereits bereits gut dokumentiert ist. REEs, die mit terrrestrischen, Fe-reichen, ausgeflockten organischen Kolloiden oder marinen, authigen gebildeten Fe-Mn Überzügen assoziiert sind, könnten beträchtlich zu den REE Gehalten beitragen. Schwache, in auf NASC normalisierten REE-Diagrammen erkennbare Ce-Anomalien von zwei Proben, lassen einen marinen Einfluß vermuten.

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With 5 Figures     

Stratigraphic status,age, and paleobathymetry of the Grey shale Member,Dalmiapuram Formation,Cauvery Basin,India

Grey shale Member of the Dalmiapuram Formation, Ariyalur Group, Cauvery Basin, India was studied for its stratigraphic position, age, and paleobathymetry with a re-look into the lithological relationship and foraminifer assemblages in the deepened limestone mine excavations at M/s Dalmia Cements, Dalmiapuram. Twenty grey shale samples from Kovandankurchchi (pit-4) and Kallakkudi mines yielded diversified calcareous, benthic, and rare index planktic foraminifera. The foraminiferal assemblages suggest a latest Albian age and middle neritic depositional conditions. The abundance of kaolinite and smectite clay minerals relate to warm/humid climate which corroborate with rising relative sea level during grey shale deposition. The grey shale occurs in patches within the marl bedded limestone member which exhibits cyclic deposition of limestone and marl. The limestone mine sections demonstrate that the grey shale forms part of basal marl bedded limestone, directly overlying the coral algal limestone. The present study demonstrates that the grey shale outcrops in Dalmiapuram Formation should be placed stratigraphically as part of marl bedded limestone. The member status for grey shale which is current usage stands discounted.     

Sources of rare earth elements in Appin Group limestones,Dalradian, north-east Scotland

Summary Rare earth elements (REE) have been determined in 15 samples from three metamorphosed limestone units of the Appin Group of the Dalradian of north-east Scotland. Total REE contents range from about 7 to about 50 ppm and the light REEs are slightly enriched compared with REE in the North American Shale Composite (NASC). In the more impure limestones, the dominant control on REE content was the clay mineral content in siliciclastic impurities derived from terrestrial sources. In the purer limestones, the correlation between REEs and iron is consistent with the well-documented relationship between iron and REEs in the aqueous environment. REE associated with terrestrial, iron-rich, flocculated organic colloids or marine, authigenic iron-manganese coats may well have contributed significantly to the REE contents. Weak Ce anomalies on NASC-normalised, REE variation diagrams in two samples with very low REE contents suggest a marine influence on the REE distribution.

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Die Quelle von seltenen erden in kalken der Appin Gruppe, Dalradians, NE Schottland

Zusammenfassung An 15 Proben aus metamorphen Kalken der Appin Gruppe der Dalradians NE Schottlands wurden die Seltenen Erden (REE) bestimmt. Der Gesamtgehalt an REE variiert von 7 bis 50 ppm, wobei die leichten REE im Vergleich zum North American Shale Composite (NASC) leicht angereichert sind. In unreinen Kalken wird der REE-Gehalt vom Tonmineralanteil der silikatisch-klastischen Verunreinigungen, die einer terrestrischen Quelle entstammen, kontrolliert. In reinen Karbonatgesteinen besteht eine Korrelation zwischen den REE und Fe, eine Beziehung, die für ein wässriges Milieu bereits bereits gut dokumentiert ist. REEs, die mit terrestrischen, Fe-reichen, ausgeflockten organischen Kolloiden oder marinen, authigen gebildeten Fe-Mn Überzügen assoziiert sind, könnten beträchtlich zu den REE Gehalten beitragen. Schwache, in auf NASC normalisierten REE-Diagrammen erkennbare Ce-Anomalien von zwei Proben, lassen einen marinen Einfluß vermuten.

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The Managing Editor regrets that the complete text of this paper has already been published in Mineral Petrol 49: 27–44 (1993)     

藏北羌塘盆地晚侏罗世海相油页岩生物标志物特征、沉积环境分析及意义

胜利河油页岩位于青藏高原腹地的羌塘盆地,具单层厚度薄、区域延伸长的特点,为羌塘盆地新发现的又一处海相油页岩.采用GC-MS(IRMS)分析方法对该油页岩进行了研究,结果表明,胜利河油页岩(11层以及13层)含有丰富的正烷烃、类异戊二烯烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC15、nC16为主峰碳,轻烃组分占有绝对优势,OEP值0.96～0.97,接近平衡值1.00,Pr/Ph为0.57～0.75,显示弱的植烷优势;萜烷丰度顺序为五环三萜烷》三环萜烷》四环萜烷;规则甾烷呈不对称的"V"字型分布,表现为C27》C29》C28的分布特征.这些特征与剖面中其他岩性的生物标志物特征存在一定的差异,9层泥晶灰岩C21-/C21 值为0.86,轻烃优势并不明显;14层泥灰岩C21-/C21 值为0.41,具有明显的重碳优势;9层泥晶灰岩以及12层泥灰岩规则甾烷呈C29》C27》C28的特征也与油页岩层存在显著的差异.这些差异不仅反映了油页岩层与其他岩性间生物母源输入的差异,也反映了他们之间沉积环境的不同.胜利河地区油页岩的形成是综合因素控制的结果,古地理变化、海平面升降、生物群差异以及气候的变化均对该区油页岩的形成有一定的影响.     

Geochemical variations of major,trace, rare earth elements in some Gondwana and Eocene coals of India with a comparison of their germanium,lithium, and mercury content

The geochemistry of major, trace, rare earth elements (REEs), with special reference to Ge, Li, and Hg in selected Gondwana and Eocene coals, has been studied. Major oxide and trace element ratios have been utilised to compare the tectonic setting, provenance of source rocks, and paleoweathering conditions that prevailed the during formation of these coals. The Gondwana coals have a higher mean mercury and ash content (244.5 μg/kg and 17.2 %, respectively) than the Eocene coals (142.1 μg/kg, 8.9 % respectively). The major oxides, SiO₂, Fe₂O_3, and Al₂O_3, in Gondwana and Eocene coals, are enriched relative to the upper continental crust (UCC), Chinese and American coals. The UCC normalized trace element concentration coefficients of the Gondwana and Eocene coals show enrichment in Ge, Se, Th, Co, Mo, Sn, W, and Li. The mean Ge and Li concentrations (mg/kg) in Gondwana (106.7, 154.7) and Eocene (120.0, 252.6) exceed the corresponding values in world coal (2.2, and 12). The Rajmahal coals have the highest mean Ge concentration (168.8 mg/kg) among the Gondwana coals while Eocene coals from East Jaintia Hills have the highest mean value (343.7 mg/kg). The Gondwana coals have a higher mean As concentration (3.5 mg/kg) in comparison to the Eocene coals (1.9 mg/kg). The mean of the rare earth elements in Gondwana (24.1 mg/kg) is higher than that in Eocene coals (11.3 mg/kg) and these values are less than the World coals (68.5 mg/kg). Both the Gondwana and Eocene coals are enriched in light rare earth elements (LREEs). However, among the Eocene coals, the Meghalayan coals show REE enrichment in comparison to Assam coals. Both the Gondwana and Eocene coals were formed in warm and humid climates under oxic conditions with moderate weathering of the source rocks.     

辽东湾东南部海域柱状沉积物稀土元素地球化学特征与物源识别

对辽东湾东南部海域LDC30孔沉积物稀土元素（REE）、粒度等指标进行了分析,研究了其沉积物中稀土元素组成特征及其控制因素,并对其物质来源进行了探讨。结果表明,LDC30孔沉积物ΣREE平均值为149.49 μg/g,略高于黄海和东海,但是低于渤海和南海,并且低于全球沉积物ΣREE的平均值。研究区沉积物REE配分模式表现为明显的轻稀土富集、重稀土相对亏损;δEu的平均值为0.71,为中度亏损,δCe无异常;轻稀土与重稀土之间的分异作用较强,且轻重稀土内部分异明显。根据沉积物REE垂向变化特征,可将LDC30岩芯以51cm为界划分为两段,上段（0~51 cm）ΣREE含量随着深度的减小而呈增加的趋势,下段（51~99 cm）ΣREE含量在垂向上没有明显的波动变化,并且上段较下段稀土分异明显。δCe整体上比较稳定,但是在上段（0~51 cm）呈现下降的趋势。δEu垂向上也相对稳定的趋势。该孔沉积物REE参数与粒度之间无明显的相关性,REE组成不受粒度的控制,但重矿物对REE的组成和分布状况有重要的影响。LDC30孔沉积物物质来源比较稳定,并且具有强烈的陆源特征,其沉积物主要来源于辽东湾北部河流（大辽河、小凌河、双台子河等）,同时辽东湾西部河流滦河可能对LDC30孔上段沉积物有一定贡献。     

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

羌塘盆地胜利河油页岩有机地球化学特征及意义

通过对藏北羌塘盆地胜利河地区2008年新发现的油页岩剖面进行系统采样和GC—MS分析,结果显示该地区油页岩具有较高C29ααα20S/ααα(20S+20R)（0.38~0.44）、C29αββ/(ααα+αββ)（0.37~0.47）和C3122S/(22S+22R)（0.52~0.59）比值,表明其有机质已进入生油阶段。分析的油页岩样品具有较高的C27甾烷含量（32.82%~43.6%）和较高4 甲基甾烷/规则甾烷（0.04~0.22）、甾/藿（0.80~1.04）比值,显示浮游植物为主的生物母源对油页岩的贡献。此外,油页岩具有较高的γ 蜡烷指数（0.34~0.50）、C35升藿烷指数（0.076~0.102）和较低的Pr/Ph比值（0.32~0.49）,表明胜利河地区油页岩沉积期水体处于相对闭塞还原和盐度较高的沉积环境。     

Limestone–marl alternations as environmental archives and the role of early diagenesis: a critical review

Limestone–marl alternations and other micritic calcareous rhythmites have long appealed to sedimentologists, as they appeared to directly reflect high-frequency environmental change. In particular, when orbital forcing gained popularity amongst sedimentologists and paleoclimatologists in 1980s, such rhythmites seemed to offer an ideal tool for high-resolution chronostratigraphy and environmental reconstruction. However, in spite of the fact that orbital forcing has become a routine interpretation of calcareous rhythmites, and that the processes of formation of calcareous rhythmites are considered well understood, research in the past 10 years again has questioned their primary origin and their direct interpretability. Detailed petrographic, paleontological, and geochemical data from numerous successions through geological time provided the basis for testing whether or not the regular alternation of limestone beds and marl or shale interlayers represents bimodally fluctuating environmental conditions in a direct way. In particular, these data, supplemented by box model simulations, imply that post-depositional alteration (diagenesis) has the potential to not only seriously distort primary environmental signals, but also to mimic primary signals. This questions the use of micritic calcareous rhythmites for high-resolution chronostratigraphy and for environmental interpretations where independent data of diagenetically inert parameters are not available. Diagenetic changes appear to have a yet widely underestimated influence on the appearance of limestone–marl alternations and other calcareous rhythmites. The aim of the present review is to summarize new approaches and give an overview of our research results in this field of the past decade. This review also aims at pointing to still enigmatic aspects that need to be addressed before the interpretation of micritic calcareous rhythmites can be considered a reliable tool for high-resolution chronostratigraphy and paleoenvironmental interpretation. “This difference [between shale and limestone] does not find definite expression in the chemical composition but appeals to the eye.” Gilbert (1895)     

东胜煤田侏罗系延安组煤中稀土元素地球化学特征

采用中子活化分析方法（INAA）测定了鄂尔多斯盆地东北部东胜煤田侏罗系延安组煤中稀土元素（REE）的含量,绘制了稀土元素分布类型曲线并计算了多种化学参数.在对REE的地球化学环境和地球化学特征分析的基础上,得出以下结论：①侏罗纪低灰低硫煤中REE的含量较低,且普遍低于华北盆地石炭二叠纪低灰低硫煤中的REE含量.②侏罗纪煤中的REE主要来自于物源区的陆源碎屑.东胜煤田北部靠近物源区,因此REE含量较南部高,且REE含量与灰分产率和SiO2含量有一定的相关性.③侏罗纪煤中REE的分布类型主要取决于母岩.除两个样品外,其他煤样普遍存在Eu负异常,无正Ce异常存在.④与其他岩石相比,煤中REE的分布类型极其复杂,原因在于开放盆地体系的煤中物质不断的改变和再分配.     

Mineralogical and elemental variation of coal from Alberta, Canada: an example from the No. 2 seam, Genesee Mine

Mineralogy and elemental contents were determined on 18 samples from a vertical profile of the No. 2 seam, Genesee mine, AB. The samples analyzed consist of coal, coaly shale, shaly coal, carbonaceous shale, shale, mudstone and siltstone. Proximate analysis was determined on all samples. Elemental analyses were determined by instrumental neutron activation analysis (INAA) for all elements except As, B, Cd, Hg, Mo, Pb, Se (Atomic Absorption) and B, Ba, Be, Co, Cr, Cu, Li, Mn, Nb, Sr and V (inductively coupled plasma-emission spectroscopy, ICP-ES). Samples were low temperature ashed (LTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF) were used to determine quantitative major mineralogy. Accessory mineralogy was determined with Scannining Electron microscope/energy dispersive X-ray analyzer (SEM/EDX) on four samples. In general, the coals in the Genesee mine are within the low end of the range for trace element contents given by Swaine [Swaine, D.J., 1990. Trace Elements in Coal. Butterworths, London, 278 pp.] for most coals. High contents of Cr (9–2620 ppm) and Ni (1–1440 ppm) can be related to an increased amount of a Cr–Ni–Fe oxide (chromite–magnetite?) likely derived from ultrabasic diatremes in the Golden-Columbia Icefields, BC area. The No. 2 seam of the Genesee mine can be divided into two geochemical cycles on the basis of mineralogy, trace element contents and rare earth element (REE) behavior. Cycle I consists of quartz, calcite and kaolinite, lower trace element contents, REE slightly enriched in high rare earth elements (HREE), and thick coal with few partings. Cycle II consists of quartz, calcite, kaolinite, illite, mixed layer and/or expandable lattice clays, feldspar, gypsum, calcium aluminum sulfate hydrate, clinoptilolite, calcite and diopside, higher trace element contents, REE slightly enriched in light rare earth elements (LREE) and thin coal with a greater frequency of partings. The differences between the two geochemical cycles can be accounted for by a decreasing stability of the peat-forming environment resulting from an increasing fluvial influence and volcanogenic input.     

长江主要支流与干流沉积物的REE组成

系统采集了长江主要支流与干流从上游到下游不同地区的河漫滩沉积物样品,用1 M盐酸淋滤处理研究了REE在不同相态中的组成特征。研究表明,长江沉积物中REE主要赋存于酸不溶相中,约占总含量的70%。不同REE的酸提取效率不同,酸溶相明显富集REE,主要受磷灰石等磷酸盐矿物和部分Fe-Mn氧化物矿物的控制。主要赋存于粘土矿物中的不同轻稀土元素在酸溶相中百分比接近,而富重稀土元素的重矿物可以明显影响REE在不同相态中的组成和不同地区河流沉积物中REE的配分特征。长江支流沉积物的REE组成变化大于干流,流域源岩组成差异是控制REE组成的基本因素,但干流和支流沉积物全样与酸不溶相的REE配分模式基本类似,反映了各自流域风化上陆壳的平均组成。尽管一些支流对邻近干流沉积物的REE组成贡献较大,但总体上干流样品代表了不同支流水系沉积物的混合,尤其是下游近河口地区细粒级沉积物样品的酸不溶组分可以代表长江入海颗粒物的平均REE组成,用于示踪判别东部边缘海长江沉积物的源汇过程。