Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop—Zones A–C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite–smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.     

Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province,south China

The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the former is greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC content is larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formation of an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content in shale. In this study, we try to establish relations between outcrop samples and core samples, in order to better understand the underground characteristics of shale reservoir.     

Geochemistry of carboniferous shales of the Sardar Formation,east central Iran: Implication for provenance,paleoclimate and paleo-oxygenation conditions at a passive continental margin

The Sardar Formation (Carboniferous) has a lithological variation that is characterized by sandstone, shale and limestone members. Shales of the Sardar Formation from the east central Iran have been analyzed for major elements and a number of trace elements. The shales of Sardar Formation are rich in quartz minerals and clay minerals of the bulk minerals. Clay minerals of shales are composed of illite, kaolinite and slightly montmorillonite. SiO₂ versus K₂O/Na₂O diagram shows these shales plotted in the passive continental margin or cratonic field. Geochemical data suggest high acidic source rocks similar to granite and intermediate igneous rocks. CIA and ICV suggest semi-humid climatic conditions during depositions and indicate high chemical weathering in the source area. The geochemical parameters such as V/Cr, Ni/Co and Cu/Zn ratios indicate that these shales were deposited in oxic environment.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

Mobilization and re-distribution of major and trace elements during extreme weathering of basalt in Hainan Island, South China

Major, trace and organic elements of a laterite profile developed on Neogene basalts in northern Hainan Island, South China were reported in this paper, the aim of which was to investigate element mobilization and re-distribution during extreme weathering. The results indicate that most of the elements have been mobilized and transferred downwards along the profile by aqueous solution. Organic matter (OM) can significantly improve the transport of insoluble elements. Among all the elements, Th is the least mobile. As for the general conservative elements during incipient chemical weathering, such as Fe, Ti, Zr, Hf, Nb and Ta, the removals are up to 20-40% in the upper profile. However, these elements behave as conservatively as Th in the lower profile. In the middle profile, oxic environment occurs, accompanied with significant OM decomposition. The Mn and Ce transferred downward are readily oxidized into insoluble Mn(IV) and Ce(IV) and precipitate in the oxic front. Important OM decomposition decreases the capacity of transfer of insoluble elements in aqueous solution. Consequently, Al significantly precipitates in the oxic front, and REEs, with the exception of Ce, precipitate largely in the OM-depleted layers. Co and U are also concentrated in the oxic front in association with Mn and Ce, respectively. However, Cr shows a negative correlation with Mn because its response to redox condition changes is reversed from that of Mn. Mn oxides/hydroxides, Fe oxides/hydroxides and secondary phosphate minerals other than clay minerals are potential hosts for REEs except for Ce in the profile; REEs with high concentrations in the profile seem closely associated with Mn oxides/hydroxides. Remarkable, highly correlated, Ce and Gd anomalies are observed in the profile. Ce anomalies are caused by Ce precipitation in the oxic environment and successive decomposition of organic matter. Gd anomalies are likely to have resulted from lower stability constants of Gd-OM complexes compared to those of neighboring REEs. The overall elemental behaviors in this profile suggest that organic matter plays a very important role in the mobilization and re-distribution of the elements during extreme weathering.     

Geological and geochemical characteristics in the paleo-weathering crust sedimentary type REE deposits,western Guizhou,China

A supergene REE deposit closely interrelated with the weathering of the Emeishan basalt formation was produced in the Xuanwei formation, the overlying stratum of the late Permian Emeishan basalt formation in West Guizhou, China. The host strata consist primarily of offwhite kaolinite clay rock and/or grayish black carbonaceous shale. Mineralogical analyses reveal that kaolinites are the major minerals in REE ores with small amounts of smectite, illite, boehmite, hornblende, pyrophyllite, calcite, dolomite and/or iron-bearing minerals, with a certain proportion of feldspar, quartz crystal debris and noncrystal debris. Geochemical analyses reveal high enrichment of trace elements like Cu, Nb, Ta, Zr and Hf. The host strata feature considerable lithological variability, close interrelation of the REE grade with the lithology and uneven spatial distribution of the REE ores, which are mostly found in Lufang, Maojiaping and Zhangsigou profiles of Weining County and can be as thick as 20 m. Of the five stratigraphic profiles, 48% have their whole-rock ∑REE higher than 1000 ppm. The REE in this framework consists primarily of ion adsorbed phases and REE-rich residual independent mineral phases. Comprehensive analyses suggest that the source may not only include the Emeishan basalt, but the intermediate acid volcanic rocks evolved from the Emeishan basalt in the later periods; the hydrothermal alteration subsequently imposed on the host strata might have boosted the mineralization of the rare earth. The preliminary genetic model should have been: the denudation product from the weathering of the parent rock was migrated to the sea-continental margin at the continent side carrying huge quantities of REE with it and was preserved by the quick marine transgression. The host strata consist primarily of kaolinite clay rock and/or carbonaceous shale, which are so far believed to be a sedimentary type REE deposit closely interrelated with weathering effect.     

Trace metal distribution and mobility in drill cuttings and produced waters from Marcellus Shale gas extraction: Uranium,arsenic, barium

Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg⁻¹, respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L⁻¹) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals.Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates.     

Adsorption of pyridine by combusted oil shale

Large volumes of solid waste material will be produced during the commercial production of shale oil. An alternative to the disposal of the solid waste product is utilization. One potential use of spent oil shale is for the stabilization of hazardous organic compounds. The objective of this study was to examine the adsorption of pyridine, commonly found in oil shale process water, by spent oil shale. The adsorption of pyridine by fresh and weathered samples of combusted New Albany Shale and Green River Formation oil shale was examined. In general, pyridine adsorption can be classified as L-type and the isotherms modeled with the Langmuir and Freundlich equations. For the combusted New Albany Shale, weathering reduced the predicted pyridine adsorption maximum and increased the amount of pyridine adsorbed at low solution concentrations. For the combusted Green River Formation oil shales, weathering increased the predicted pyridine adsorption maximum. The pyridine adsorption isotherms were similar to those produced for a combusted Australian oil shale. Although adsorption can be mathematically described by empirical models, the reduction in solution concentrations of pyridine was generally less than 10 mg/l at an initial concentration of 100 mg/l. Clearly, the observed reduction in solution pyridine concentrations does not sufficiently justify using spent oil shale as a stabilizing medium. However, data in the literature suggest that other organic compounds can be effectively removed from solution by spent oil shale and that adsorption is dependent on process conditions and organic compound type.     

Speciation and weathering of selenium in upper cretaceous chalk and shale from South Dakota and Wyoming, USA

In geologic materials, petroleum, and the environment, selenium occurs in various oxidation states (VI, IV, 0, -II), mineralized forms, and organo-Se complexes. Each of these forms is characterized by specific chemical and biochemical properties that control the element’s solubility, toxicity, and environmental behavior. The organic rich chalks and shales of the Upper Cretaceous Niobrara Formation and the Pierre Shale in South Dakota and Wyoming are bentoniferous stratigraphic intervals characterized by anomalously high concentrations of naturally occurring Se. Numerous environmental problems have been associated with Se derived from these geological units, including the development of seleniferous soils and vegetation that are toxic to livestock and the contamination of drinking water supplies by Se mobilized in groundwater.This study describes a sequential extraction protocol followed by speciation treatments and quantitative analysis by Hydride Generation-Atomic Absorption Spectroscopy. This protocol was utilized to investigate the geochemical forms and the oxidation states in which Se occurs in these geologic units. Organic Se and di-selenide minerals are the predominant forms of Se present in the chalks, shales, and bentonites, but distinctive variations in these forms were observed between different sample types. Chalks contain significantly greater proportions of Se in the form of di-selenide minerals (including Se associated with pyrite) than the shales where base-soluble, humic, organo-Se complexes are more prevalent. A comparison between unweathered samples collected from lithologic drill cores and weathered samples collected from outcrop suggest that the humic, organic-Se compounds in shale are formed during oxidative weathering and that Se oxidized by weathering is more likely to be retained by shale than by chalk. Selenium enrichment in bentonites is inferred to result from secondary processes including the adsorption of Se mobilized by groundwater from surrounding organic rich sediments to clay mineral and iron hydroxide surfaces, as well as microbial reduction of Se within the bentonitic intervals. Distinct differences are inferred for the biogeochemical pathways that affected sedimentary Se sequestration during periods of chalk accumulation compared to shale deposition in the Cretaceous seaway. Mineralogy of sediment and the nature of the organic matter associated with each of these rock types have important implications for the environmental chemistry and release of Se to the environment during weathering.     

鄂尔多斯盆地黄陵北部延安组页岩气勘探潜力分析

鄂尔多斯盆地中南部发育有侏罗系延安组第二段和第三段陆相暗色厚层泥岩层系,矿物成分以石英、黏土为主,石英43%~56%,黏土矿物29%~33%。总有机碳(TOC)1.63%~3.89%,有机质成熟度R_o为0.59%~0.60%,含气量(CH₄)0.25~0.85 m3/t,等温吸附实验表明延安组泥岩的甲烷吸附能力与总有机碳含量呈正相关关系。泥岩处于生物成因气阶段,具备页岩气形成的基本地质条件,并可对比美国密歇根盆地Antrim页岩和伊利诺斯盆地的New Albany页岩的地质条件。为查清黄陵北部侏罗系延安组页岩气的勘探潜力,通过分析勘查和化验测试资料,对其页岩气勘探潜力进一步评价认为:黄陵北部延安组泥岩分布范围和厚度较大,已进入生物成因气和热催化生气的中间阶段,有机质丰度较高,具备形成页岩气的成藏条件,页岩气潜力巨大。      

Geochemistry of phosphate bearing sedimentary rocks in parts of Sonrai block,Lalitpur District,Uttar Pradesh,India

Major, trace and rare earth elements of phosphatic rocks around Sonrai block of Paleo-Mesoproterozoic age having phosphatic breccia, quartzite, shale, sandstone, limestone and ironstone, have been determined to evaluate their correlation, relationship with the phosphorus content, the nature of possible substitution of various elements and regional distribution pattern over the area. The study indicates that the number of elements is substituted in the apatite structures; few of them are associated with phosphate and carbonate minerals. The variable concentration of major, trace and rare earth elements in the phosphatic rocks has been influenced by various physico-chemical processes involved during weathering and leaching of the source rocks. The distribution of the major, trace and rare earth elements is controlled by the environmental variations in the sediment water interface. The majority of trace elements were mainly influenced by the principle adsorbents like the phosphate minerals in addition to clay, iron oxides and silicate minerals. The PAAS normalized REE patterns of Sonrai block of phosphorites are characterized by negative Ce anomalies and Positive Eu anomalies. It is inferred from the distribution and interrelationship of major, trace and rare earth elements that the deposition of phosphate minerals might have occurred in highly oxidizing to slightly reducing conditions in supratidal to intertidal continental margins and shallow marine environment. The deposition was controlled by marine upwelling leading to excess charge of phosphate in certain zones of phosphogenic basins, lithologic facies variations in restricted circulations of basinal waters and electrochemical factors such as negative Eh, pH and other factors, which influenced the deposition of phosphates. The replacement, precipitation in voids and fissures and diagenesis were also important mechanisms of phosphate generation in Sonrai basin. The main source for various elements may be the minerals of cratonic mass of Bundelkhand Granitic Complex, a basement of Bijawar Basin, which also provided land derived phosphorus through weathering of the terrestrial cover.     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

Contaminants from Cretaceous black shale: I. Natural weathering processes controlling contaminant cycling in Mancos Shale,southwestern United States,with emphasis on salinity and selenium

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na₂SO₄) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m⁻²) enriches soil moisture in Na and residual SO₄. Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.     

Solubility relationships of aluminum and iron minerals associated with acid mine drainage

The ability to properly manage the oxidation of pyritic minerals and associated acid mine drainage is dependent upon understanding the chemistry of the disposal environment. One accepted disposal method is placing pyritic-containing materials in the groundwater environment. The objective of this study was to examine solubility relationships of Al and Fe minerals associated with pyritic waste disposed in a low leaching aerobic saturated environment. Two eastern oil shales were used in this oxidizing equilibration study, a New Albany Shale (unweathered, 4.6 percent pyrite), and a Chattanooga Shale (weathered, 1.5 percent pyrite). Oil shale samples were equilibrated with distilled-deionized water from 1 to 180 d with a 1∶1 solid-to-solution ratio. The suspensions were filtered and the clear filtrates were analyzed for total cations and anions. Ion activities were calculated from total concentrations. Below pH 6.0, depending upon SO ₄ ²⁻ activity, Al³⁺ solubility was controlled by AlOHSO₄ (solid phase) for both shales. Initially, Al³⁺ solubility for the New Albany Shale showed equilibrium with amorphous Al(OH)₃. The pH decreased with time, and Al³⁺ solubility approached equilibrium with AlOHSO_4(s). Below pH 6.0, Fe³⁺ solubility appeared to be regulated by a basic iron sulfate solid phase with the stoichiometric composition of FeOHSO_4(s). The results of this study indicate that below pH 6.0, Al³⁺ solubilities, are limited by basic Al and Fe sulfate solid phases (AlOHSO_4(s) and FeHSO_4(s)). The results from this study further indicate that the acidity in oil shale waters is produced from the hydrolysis of Al³⁺ and Fe³⁺ activities in solution. These results indicate a fundamental change in the stoichiometric equations used to predict acidity from iron sulfide oxidation. The results of this study also indicate that water quality predictions associated with acid mine drainage can be based on fundamental thermodynamic relationships. As a result, waste management decisions can be based on waste-specific/site-specific test methods.     

Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale,southern Ordos Basin,China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.     

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

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

Geology,geochemistry and mineralogy of the lignite-hosted Ambassador palaeochannel uranium and multi-element deposit,Gunbarrel Basin,Western Australia

The Ambassador U and multi-element deposit occurs on the SW margin of the Gunbarrel Basin, Western Australia. Low-grade, flat-lying U mineralization averaging about 2 m thick at 0.03% U occurs in lignites at the redox front at the base of the weathering profile within a laterally extensive palaeochannel network. Uranium is principally associated with organic matter within the lignitic matrix, although rare discrete U minerals, such as coffinite and uraninite, are also present. The lignite is also enriched in a suite of other elements, principally base metals and sulphur, with concentrations of 0.3 ≥ 1% Cu, Pb, Ni, Co, Zn and total rare earth elements (REE) in some samples. Other element enrichments include: Cr, Cs, Sc, Se, Ta, Ti, Th, V and Zr as detrital heavy minerals of Zr, Ti and REE (oxides and silicates) or authigenic minerals of Cu, Bi, Pb, Zn, Ni, Se, Hg, Ti, Cr, Tl, V, U and REE (sulphides, vanadates, selenides, oxides, chlorides and native metals) and diffuse lignite impregnations. The Ambassador deposit probably formed from the convergence of redox-active weathering processes to unique source/host rocks, constrained within the palaeochannel. A proximal source of U and trace elements of lamproite/carbonatite origin is probable, as constrained by U–Pb isotope and U–Th disequilibria studies. Uranium and other metals were precipitated syngenetically with organic matter as it was deposited during a humid phase in the Late Eocene. Remobilization subsequently concentrated the metals in the upper 2 m of the lignite. This may have occurred during one or more periods of weathering and associated diagenesis, with the latest episode in the last 300,000 years.     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127.9±1.4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱风化层（C3）和基岩（D）五层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显(La/Yb)N=15.6），但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过百分之五十，其次为斜长石，是风化壳中REE的重要来源。     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127. 9±1. 4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱半风化层（C3）和基岩（D） 5层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显\[(La/Yb)N=15. 6\]，但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过 50%，其次为斜长石，是风化壳中REE的重要来源。     

Content and mode of occurrences of rare earth elements in the Zagrad karstic bauxite deposit (Nikšić area,Montenegro)

Three vertical sections through the Zagrad deposit of Jurassic karst bauxite in central Montenegro have provided knowledge of the vertical distribution of major and some selected trace elements, including rare earth elements (REE). Variations in the mineralogy, particularly those hosting REE, have been studied. This has revealed the presence of authigenic mineral phases such as xenotime, mottramite and monazite (best proved using Raman microprobe analysis) as well as residual phases such as zircon, titanite and monazite. The mobility of the elements during bauxitization processes has been studied to show that the REE minerals ensure progressive concentration of these elements during removal of major elements through weathering. The similarity of normalized REE in the bauxite to the typical Post-Archean Australian Shales (PAAS) and Upper Continental Crust (UCC) profile, and the preserved Eu anomaly, are evidence that the bauxite was not derived from carbonates and represents alteration of shale, marly limestone and volcanogenic or proximal igneous sourced detritus that accumulated in the original karst landform. Mass change during bauxitization, using Ti as “index” element and compared to PAAS composition, revealed almost 100% depletion of Si and weak enrichment in Al. Deeper parts of the deposit with authigenic minerals exhibit very strong enrichment in all REE. The bauxite ores have high ΣREE contents (693.5–6953.4 ppm), especially ΣLREE contents (582.8–4882.9 ppm), while ΣHREE contents (106.6–2070.5 ppm) are much lower.