Geochemistry of soils derived from black shale, central Hunan, China

The black shale formed under anoxic conditions usually contains high concentrations of many metals. Weathering of such black shale might cause the emission of many metals. Moreover, soils derived from black shale （SBS） are believed to be affected by black shale weathering. In recent years, many studies such as Lee et al. （2002）, Woo et al. （2002）, Fang et al. （2002）, Pasava et al. （2003）, and Peng et al. （2004） have approached the heavy metal contaminations of SBS, but systematical geochemical study is rare. Presently, the SBS and its corresponding black shales （CBS） were both sampled from central Hunan （China）, and analyzed for a large number of elements, using an Elan6000 ICP-MS/AES machine at Guangzhou Institute of Geochemistry, CAS. In this paper, some preliminary results are reported. The analytical results show that the SBS in central Hunan contains very high concentrations of heavy metals such as Co, Cu, Hg, Mo, Pb, Zn, U, Th, Sb, T1, Cd, Cr, Sc, V, Sn, As, Se, and Ni.     

西天山异剥钙榴岩的地球化学研究

西天山长阿吾子的蛇绿混杂岩带的超基性岩及其伴生岩石异剥钙榴岩位于伊犁中天山板块和塔里木板块碰撞造山带.微量元素特征表明退变榴辉岩原岩成因与俯冲带环境有关.异剥钙榴岩中稀土元素和微量元素全面、大幅度降低,反映出来自于蛇纹岩化,作用于异剥钙榴岩化流体的强大的淋滤作用.因而异剥钙榴岩的稀土和微量元素特征都不能反映原始岩浆的特点,无法据此推断原始岩浆产生的大地构造环境.对退变榴辉岩的主元素和微量元素稀土元素的研究表明,长阿吾子异剥钙榴岩的原岩钙碱性玄武岩可能形成于俯冲上板片(SSZ)的岛弧环境.     

Geochemistry and mineralogy of marine and non-marine Namurian black shales from the Tansley Borehole, Derbyshire

The Namurian black shales studied have a good palaeontological control. Pyrite, illite and organic matter are higher in the marine shales, and siderite and kaolinite are higher in the non-marine shales. The distribution of the diagenetic iron minerals is attributed to anionic activities controlled by salinity. The same control could account for the observed clay-mineral distribution by differential flocculation. The major element geochemistry closely reflects the above mineral variation. Mn and Zr are higher in the non-marine shales due to siderite and zircon respectively. Co, Cr, Rb, Y and Ba are not significantly different and a detrital source, mainly clay minerals, is suggested. In the marine shales the elements Pb, Cu, V, Ni, Sr and Zn are significantly higher. Using a discriminant function analysis the palaeosalinity groups are separated and the contribution of each element to the separation is calculated. The present element locations are thought, from correlation analysis, to be pyrite and organic matter. By analogy with experimental work and modern environments, the element enrichment is mainly attributed to reactions involving organic matter and oxyhydroxide material in environments in which salinity and slow rates of sedimentation were important factors. The element enrichment cannot be related directly to seawater concentrations, unlike some black shales, and the accumulation rates for Pb and Cu are thought to be unusually high.     

Alkenones in Cretaceous black shales, Blake-Bahama Basin, western North Atlantic

We here report the discovery of unusual distributions of long-chain alkenones (C₃₇-C₄₂) in two Cretaceous black shales from the Blake-Bahama Basin, western North Atlantic. These sediments are Cenomanian (c. 95 Ma) and mid-Albian (c. 105 Ma) in age, thus significantly extending the geological range of these compounds. The precise source of these lipids is, as yet, unknown, although they may derive from an ancient ancestor of Emiliania huxleyi.     

湖南洞庭湖地区土壤中Hg的来源

Hg污染已成为全球性的环境问题,尤其是Hg对土壤的污染,因其具有隐蔽性、不可逆性和长期性的特点,对陆生生态系统构成潜在的巨大威胁,因此查明土壤中Hg的来源非常重要。运用生态地球化学填图的指导思想,对湖南洞庭湖地区土壤剖面分析和成土过程研究后发现,表层土壤中Hg含量的高低与成土母质中Hg的含量有很好的对应性,成土过程对土壤中Hg的含量也有显著的影响。     

Geochemistry of major and trace elements and Pb–Sr isotopes of a weathering profile developed on the Lower Cambrian black shales in central Hunan,China

This paper reports a geochemical study on the major and trace elements and Pb–Sr isotopes of a weathering profile developed in the Lower Cambrian black shales in central Hunan (China). Six weathering horizons were identified and sampled vertically throughout the profile. The chemical composition of the profile consists of variable concentrations of the major elements Fe₂O₃, FeO, MnO, MgO, CaO, Na₂O, and P₂O₅ and of less variable concentrations of SiO₂, TiO₂, Al₂O₃, and K₂O. The chemical change caused by weathering is estimated by mass-balance calculations, and the results show that the element mobility is characterised by substantial loss of SiO₂, FeO, CaO, K₂O, Na₂O, LOI, Cr, V, Ba, Cs, Rb, Sr, U, and Th, and moderate loss of Al₂O₃, MgO, Fe₂O₃, Ni, Cu, Pb, Tl, Sn, Sc, Ge and REE (Y). The high field strength elements TiO₂, Sn, Sc, U, Ga, Ge, Zr, Hf, Nb, and Ta were immobile during weathering. The chemical changes and the Pb–Sr isotopic data suggest that four types of chemical reactions occurred: the oxidation of sulphide minerals (e.g., pyrite) and organic carbon (OS), the dissolution of less resistant clinochlore-Ia, calcite, and P-bearing minerals (DL), the dissolution of detrital albite and microcline (DA), and the transformation of clay (TC) minerals (e.g., muscovite and illite–smectite). These chemical reactions then led to two stages of geochemical processes, an early stage of chemical differentiation and a later stage of chemical homogenisation. The chemical differentiation dominated by the OS, DL, and DA reactions, led to the leaching of mobile elements (e.g., MgO, Na₂O, K₂O, P₂O₅, Sr, and REE) and the redistribution of some less mobile elements (e.g., SiO₂ and Al₂O₃). In contrast, the chemical homogenisation, which was caused by TC reactions, led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil. Soils derived from black shales in South China might result from the above two geochemical processes.     

Lithofacies and depositional characteristics of gas shales in the western area of the Lower Yangtze,China

The Lower Yangtze is considered as a potentially productive shale gas area in China, but only limited research has thus far been carried out there. On the basis of a detailed investigation of fourteen outcrops, eight lithofacies in the Hetang Formation (510–541 Ma), the Gaojiabian Formation (430–443.4 Ma), the Gufeng Formation (270–281 Ma) and the Dalong Formation (252–263 Ma) have been identified: silicalite, siliceous non‐calcareous mudstone, siliceous shale, carbonaceous shale, calcareous mudstone, silty–shaly interlaminated mudstone, siltstone and limestone. Three types of fossils were also found in the four formations: sponge spicules, radiolarians and graptolites. Moreover, four key outcrops of the fourteen were suitable for more additional detailed analyses and interpretation of their depositional environments and plausible sequence of the stratigraphic system tracts. As a result, the four potential shale gas formations were all divided into third‐order sea‐level sequences. Every third‐order sequence was further divided into four system tracts, corresponding to an early transgressive system tract (ETST), a late transgressive system tract (LTST), an early highstand system tract (EHST) and a late highstand system tract (LHST). On the basis of the interpretation of the lithofacies and depositional environments in the western area of the Lower Yangtze, sediments can be related to hydrothermal and biological processes, terrigenous clastic input and calcium compensation. These processes were interpreted to occur in a sequential order that we divide into three stages. The ETST period was the first stage, in which hydrothermal upwelling from the open ocean produced a siliceous lithological combination. During the second stage corresponding to the LTST + EHST, our results suggest that some biological communities in the stable deep water provided plenty of organic‐rich matter. The LHST period was the third stage, in which terrigenous clastic material was deposited close to the land, and some carbonate sediments began appearing near the platform. Copyright © 2014 John Wiley & Sons, Ltd.     

中、下扬子地区下寒武统黑色页岩微量元素富集特征

中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。     

康滇古陆西侧龙马溪组黑色页岩地球化学特征及其地质意义

为查明康滇古陆西侧龙马溪组黑色岩系的地质成因及沉积环境,指导区域页岩气勘探开发,对宁蒗盆地东南缘李子河地区龙马溪组岩层开展了详细的元素地球化学研究。结果表明,研究区硅质含量较高(SiO₂值为64.78%~96.89%),Al₂O₃与TiO₂呈正相关,SiO₂/A1₂O₃与A1₂O₃呈负相关,这种相关关系表明该区硅质岩系为非纯硅质岩,含有较高比例的陆源泥质沉积物。Al/(Al+Fe+Mn)值(0.53~0.75)、Fe/Ti值(6.38~14.96)、(Fe+Mn)/Ti值(6.40~18.20)、Si/(Si+Al+Fe)值(0.82~0.99)及Al-Fe-Mn三角图解综合显示出生物沉积硅质岩的特点。MnO₂/TiO₂值(0.005~1.20)、δCe值(0.46~0.92)、相关构造判别图解以及稀土元素分布形式特点均说明源区形成于接近大陆边缘的深水-半深水沉积环境。沉积期水体盐度指标m值(4.96~36.88)、CaO/(Fe+CaO)值(0.017~0.83)以及氧化还原指标δCe负异常、δEu正异常、Ce/La值(1.04~2.09)等元素特征指示其沉积于还原条件下低中等盐度海水环境,这种环境下适合有机质的富集和保存。高有机碳(TOC)与高硅质含量显示弱的负相关,说明生物成因硅质岩是造成高TOC的主要原因,而陆源物质硅对有机质进行稀释和破坏反而降低了TOC含量。受上述成因构造及沉积环境的影响,在宁蒗盆地李子河地区龙马溪组形成一套品质较好的富有机质烃源岩储层,具有一定的页岩气地质评价意义。     

重庆长河碥矿煤的微量元素地球化学特征

运用煤岩学和地球化学的理论和方法,对重庆长河碥矿晚三叠世须家河组煤中微量元素进行了研究。结果表明,长河碥矿各煤层中明显富集Pb,其平均值为29.58μg/g。长河碥矿煤中潜在的有害微量元素Be (5.9μg/g)、Cr (28.6μg/g)、Cu (34.06μg/g)、As (10.03μg/g)和Th (12.49μg/g)均较富集;稀土元素含量为59.79²87μg/g,均值为136.92μg/g,略高于中国煤中稀土元素总量均值(119.7μg/g),高于美国煤中的稀土元素总量均值(53.59μg/g)。8煤中稀土元素含量异常可能是地下水淋滤作用的结果。长河碥矿煤中有害微量元素主要受控于陆源物质的供给。     

湘西花桥—大江口地区推覆构造特征

湘西北地体与湘中地体碰撞拼贴带北西侧的前陆冲折带上发育一系列叠瓦状排列的逆冲推覆构造 ,向北西方向推覆 ,具双重逆冲推覆特征。叙述了该地区推覆构造的基本特征及其对中生代陆相红盆的形成、演化过程的控制和改造。     

Geochemistry of Archean shales from the Pilbara Supergroup,Western Australia

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group (ca. 3.4 Ae) and shales from the Whim Creek Group (ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition.Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ($\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}\text{≥ 7.5}$) and no or very slight Eu depletion ($\text{Eu}\text{Eu}{}^1\text{= 0.82 – 0.99}$). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.     

Geochemistry of basal Cambrian black shales and cherts from the Northern Tarim Basin,Northwest China: Implications for depositional setting and tectonic history

Black shales and thin-bedded cherts in the basal Cambrian are widespread worldwide and they carry important information on the formation of sedimentary basins and on the tectonic history. We studied the geochemical signatures of the early Cambrian black shales and bedded cherts from the Northern Tarim Basin, China, with the objectives of understanding the depositional setting of these rocks and inferring the tectonic history in the region. Twenty two black shales, ten cherts, and two nodular phosphorites were collected from two outcrops at Xiaoerbulake and Sugaitebulake in the Northern Tarim Basin, spanning vertical sections of 8.8 and 7.5 m, respectively. A suite of techniques, including field investigations, X-ray diffraction, electron microscopy, trace element, rare earth element (REE), and isotope geochemistry, were employed to characterize the geochemical signatures of these rocks. Field evidence indicates that the black shales and bedded cherts are over- and underlain by dolomites, suggesting a shallow marine depositional environment. Mineralogical and trace element data suggest that the Tarim black shales and cherts were deposited in a suboxic continental shelf environment, and hydrothermal activity may have extracted certain trace elements from mafic continental crust and concentrated them in the sedimentary basin. REE characteristics for the cherts are very similar to those that are known to be deposited in pelagic ocean floor settings, suggesting that the hydrothermal fluids may be derived from the infant southern Tianshan Ocean in the north of the Tarim Basin. Os isotope signatures at the time of deposition (¹⁸⁷Os/¹⁸⁸Os_i = 1.1–2.7) are typical of crustal signatures, and the radiogenic Os isotope signatures rule out the mantle as a possible source of Os and other metals. A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ε_Nd is consistent with upper crust-derived basin sediments that contain a variable contribution of hydrothermal fluids possibly derived from ancient mafic continental crust. These trace element, REE, and isotope systematics collectively suggest that incorporation of hydrothermal fluids derived from ancient, mafic continental crust combined with deposition in relatively reducing conditions may have controlled the chemical and isotopic compositions of these rocks. We infer that the hydrothermal fluid was carried to the continental shelf by upwelling during the initial stages of formation of the southern Tianshan Ocean, where the fluid interacted with thinned, mafic crustal basement lithologies and was subsequently incorporated into the black shales and bedded cherts in the Northern Tarim Basin. This study provides important geochemical evidence for the creation of the Tianshan Ocean, which is a result of break-up of the Rodinia Supercontinent during the early Cambrian.     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.     

Carbon and sulfur isotopic compositions of Early Cambrian black shales,NW Hunan,China: Implications for the Paleoceanographic sedimentary environment

In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.     

Petrology of rodingite derived from eclogite in western Tianshan, China

This study reports a new rodingite type which was derived from eclogite enclosed in the ultramafic rocks of Changawuzi ophiolites, western Tianshan, China. Based on petrographical investigations, rodingite, partial rodingitized rock and completely rodingitized rock are characterized in this paper. These rocks show a continuous variation in their bulk compositions, mineralogy and their textural properties from eclogite to rodingite. The completely rodingitized rocks can be further divided into prehnite rodingites, hydrogrossular‐diopside rodingite and vesuvianite rodingites on the basis of the mineral assemblage and textural character. The chemical potential path of μ(SiO₂)–μ(CaO/MgO) can be used to constrain the evolution of two stages of rodingitization. The first rodingitization possibly started under conditions of 410–430 °C and 7–9 kbar at upper greenschist facies, and resulted from a secondary serpentinization during exhumation of the subducted slab. A second and pervasive rodingitization took place under conditions of 250–350 °C and 2–10 kbar from greenschist to subgreenschist facies. The P–T path presented shows a retrograde evolution from eclogite to rodingite. We conclude that the process of rodingitization may also take place under subduction zone conditions in addition to its more common occurrence under ocean‐floor metamorphic conditions.     

Geochemistry of black shales from the Neoarchaean Sandur Superterrane, India: First cycle volcanogenic sedimentary rocks in an intraoceanic arc-trench complex

The ∼2.7 Ga Sandur Superterrane (SST), of the western Dharwar craton, is a collage of greenstone terranes having distinct lithotectonic associations; volcanic associations are prevalent. Fine-grained metasedimentary rocks, which are optimal for provenance studies, are sparse in greenstone terranes of this craton. However, extensive shale sequences are present in the eastern volcanic terrane (EVT) and the eastern felsic volcanic terrane (EFVT) of the SST. Within the EVT, the black shales are stratigraphically associated with black cherts, metabasalt and banded iron formation (BIF), and underlain by greywackes. Shales have compositions of tholeiitic basalt in terms of TiO₂, Cr, Co, Ni, V, and Sc contents, and plot near the arc basalt endmember on the Th/Sc versus Sc mixing hyperbola. In contrast, Archean average upper continental crust of Taylor and McLennan [Taylor, S.R., McLennan, S.M., 1985. The Continental crust: Its Composition and Evolution. Blackwell, Oxford, 307p.; Taylor, S.R., McLennan, S.M., 1995. The geochemical evolution of the continental crust. Rev. Geophys.33, 241-265], plots mid-hyperbola indicative of bimodal arc magma provenance. Accordingly, the Sandur shales likely had a catchment in an oceanic arc or back-arc dominated by tholeiitic basalts. Specifically, Nb/Th ratios 1.5-2.5 in shales are close to those of Archean arc basalts (1-4), so a plateau or ocean island basalt source, where Nb/Th >8, can be ruled out. Compositionally, cherts are shale highly diluted by silica, with positive Eu anomalies, and are interpreted to be hydrothermal sediments precipitated from reduced fluids during periods of limited siliciclastic input. In the shales, variable SiO₂ and Fe₂O₃ contents, depletions of MnO, MgO, and Na₂O, and positive to negative Eu anomalies, but gains of K relative to arc basalt compositions, are interpreted as due to hydrothermal alteration. Greywackes underlying the shales have two compositions. Type I is similar to the shales, whereas Type II has fractionated REE with negative Eu anomalies consistent with a cratonic granitoid catchment [Manikyamba, C., Naqvi, S.M., Moeen, S., Gnaneswar Rao, T., Balaram, V., Ramesh, S.V., Reddy, G.L.N., 1997a. Geochemical heterogeneities of metagreywackes from the Sandur schist belt: implications for active plate margin processes. Precambrian Res. 84, 117-138]. Collectively, the results are in keeping with an intraoceanic arc outboard of a continental margin. During transgression the trench has a low energy shale facies with dominant arc contribution, but for regression high energy greywackes are deposited from a cratonic provenance.     

Geochemistry of the Yutangba Se Deposit in Western Hubei, China

1IntroductionThecontentsofSeinthecrustareextremelylow ,onlyabout0 .0 5mg/kg .Innatureitishardtoformindependentminerals,insteaditisdispersedinothermineralsandmedia.Althoughitscon tentsarefarhigherthanthoseofTeinthecrust,seleniumisusuallydispersedinsulfidesinitsas cendingandformingprocesses (D’yachkovaandKhodakovskiy ,1 968) .Thisisthereasonwhyse leniummineralsarefarlessthantelluriummineralsandsulfidesinnature (Simonetal.,1 997) .Forthisreason ,thegeochemicalstudyofseleniumdidnotattractanyat…     

Geochemistry of black shales from the Lower Cretaceous Paja Formation,Eastern Cordillera,Colombia: Source weathering,provenance, and tectonic setting

The major and trace element characteristics of black shales from the Lower Cretaceous Paja Formation of Colombia are broadly comparable with those of the average upper continental crust. Among the exceptions are marked enrichments in V, Cr, and Ni. These enrichments are associated with high organic carbon contents. CaO and Na₂O are strongly depleted, leading to high values for both the Chemical Index of Alteration (77–96) and the Plagioclase Index of Alteration (86–99), which indicates derivation from a stable, intensely weathered felsic source terrane. The REE abundances and patterns vary considerably but can be divided into three main groups according to their characteristics and stratigraphic position. Four samples from the lower part of the Paja Formation (Group 1) are characterized by LREE-enriched chondrite-normalized patterns (average La_N/Yb_N = 8.41) and significant negative Eu anomalies (average Eu/Eu¹ = 0.63). A second group of five samples (Group 2), also from the lower part, have relatively flat REE patterns (average La_N/Yb_N = 1.84) and only slightly smaller Eu anomalies (average Eu/Eu¹ = 0.69). Six samples from the middle and upper parts (Group 3) have highly fractionated patterns (average La_N/Yb_N = 15.35), resembling those of Group 1, and an identical average Eu/Eu¹ of 0.63. The fractionated REE patterns and significant negative Eu anomalies in Groups 1 and 3 are consistent with derivation from an evolved felsic source. The flatter patterns of Group 2 shale and strongly concave MREE-depleted patterns in two additional shales likely were produced during diagenesis, rather than reflecting more mafic detrital inputs. An analysis of a single sandstone suggests diagenetic modification of the REE, because its REE pattern is identical to that of the upper continental crust except for the presence of a significant positive Eu anomaly (Eu/Eu¹ = 1.15). Felsic provenance for all samples is suggested by the clustering on the Th/Sc–Zr/Sc and Gd_N/Yb_N–Eu/Eu¹ diagrams. Averages of unmodified Groups 1 and 3 REE patterns compare well with cratonic sediments from the Roraima Formation in the Guyana Shield, suggesting derivation from a continental source of similar composition. In comparison with modern sediments, the geochemical parameters (K₂O/Na₂O, La_N/Yb_N, La_N/Sm_N, Eu/Eu¹, La/Sc, La/Y, Ce/Sc) suggest the Paja Formation was deposited at a passive margin. The Paja shales thus represent highly mature sediments recycled from deeply weathered, older, sedimentary/metasedimentary rocks, possibly in the Guyana Shield, though Na-rich volcanic/granitic rocks may have contributed to some extent.