A new type of rare earth elements deposit in weathering crust of Permian basalt in western Guizhou, NW China

A new type of rare earth elements （REEs） deposit was discovered from the gaolinite mudstone in the weathering crust of Permian basalt, Bijie region, western Guizhou, China. It contained ∑RE2O3 0.065%-1.086%. This type of REEs deposit was widely distributed with steady horizon and thickness of 3-4 m. The ore-bearing weathering crust （kaolinite） of the three discovered REEs deposits belonged to the third episode of the Emeishan basalt eruption. The new type of REEs deposit was suggested that basalt （tuff） weathering could lead to the enrichment of the rare earth elements. Therefore, it is of important economic significance to explore REEs deposits in the weathering crust of basalt （tuffs） in Yunnan, Guizhou, and Sichuan Provinces.

RARE EARTH PARTITIONING OF GRANITOID WEATHERING CRUST IN SOUTHERN CHINA

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The Identification and Modeling of the Volcanic Weathering Crust in the Yingcheng Formation of the Xujiaweizi Fault Depression, Songliao Basin

Through the analysis of core descriptions, well-logs, seismic data, geochemical data and structural settings of the volcanic rock of the Yingcheng Formation in the Xujiaweizi fault depression, Songliao Basin, and the geological section of the Yingcheng Formation in the southeast uplift area, this work determined the existence of volcanic weathering crust exists in the study area. The identification marks on the volcanic weathering crust can be recognized on the scale of core, logging, seismic, geochemistry, etc. In the study area, the structure of this crust is divided into clay layer, leached zone, fracture zone and host rocks, which are 5-118 m thick （averaging 27.5 m）. The lithology of the weathering crust includes basalt, andesite, rhyolite and volcanic breccia, and the lithofacies are igneous effusive and extrusive facies. The volcanic weathering crusts are clustered together in the Dashen zone and the middle of the Xuzhong zone, whereas in the Shengshen zone and other parts of the Xuzhong zone, they have a relatively scattered distribution. It is a major volcanic reservoir bed, which covers an area of 2104.16 km2. According to the geotectonic setting of the Songliao Basin, the formation process of the weathering crust is complete. Combining the macroscopic and microscopic features of the weathering crust of the Yingcheng Formation in Xujiaweizi with the logging and three-dimensional seismic sections, we established a developmental model of the paleo uplift and a developmental model of the slope belt that coexists with the sag on the Xujiaweizi volcanic weathering crust. In addition, the relationship between the volcanic weathering crust and the formation and distribution of the oil/gas reservoir is discussed.

Fission Track Dating of Authigenic Quartz in Red Weathering Crusts of Carbonate Rocks in Guizhou Province

The Cenozoic evolution history of Guizhou Province, which is located on the southeastern flank of the Qinghai-Tibet Plateau, is unclear because of the lack of sedimentation records. The red weathering crusts widespread on the Yunnan-Guizhou Plateau may bear critical information about their evolution history. This work firstly determined the ages of four red weathering crusts in eastern, central and northern Guizhou. The material used in fission track dating is well-crystallized quartz occurring in many in-situ weathering crusts of carbonate rocks. The results showed that the fission track ages of quartz vary over a wide range from 1 to 25 Ma in the four profiles, significantly younger than the ages of the Triassic and Cambrian parent rocks. In combination with the evolution history of the regional geology during the period from 25 to 1 Ma, the ages of quartz can exclude the possibility that the origin of quartz has nothing to do with primary clastic minerals in parent rocks, authigenesis during diagenesis and hydrothermal precipitation or roplacement by volcanic activities. It is deduced that the well-crystallized quartz was precipitated from Si-rich weathering fluids during the weathering process of carbonate rocks. The recorded ages of quartz from the four profiles are consistent with the episodes of the planation surfaces on the Qinghai-Tibet Plateau, the forming stages of red soil in the tropics of South China, the tectonically stable periods in Guizhou, and the ages of weathering in other parts of the world during the Cenozoic era. That is to say, the ages of authigenic quartz dated by the fission track method are well feasible and credible.

Heterogeneity of Parent Rocks and Its Constraints on Geochemical Criteria in Weathering Crusts of Carbonate Rocks

Owing to the low contents of their acid-insoluble components, carbonate rocks tend to decrease sharply in volume in association with the formation of weathering crust. The formation of a 1 m-thick weathering crust would usually consume more than ten meters to several tens of meters of thickness of parent rocks. The knowledge of how to identify the homogeneity of parent rocks is essential to understand the formation mechanism of weathering crust in karst regions, especially that of thick-layered red weathering crust. In this work the grain-size analyses have demonstrated that the three profiles studied are the residual weathering crust of carbonate rocks and further showed that there objectively exists the heterogeneity of parent rocks in the three studied weathering crusts. The heterogeneity of parent rocks can also be reflected m geochemical parameters of major elements, just as the characteristics of frequency plot of grain-size distribution. Conservative trace element ratios Zr/Hf and Nb/Ta are proven to be unsuitable for tracing the heterogeneity of parent rocks of weathering crust, but its geochemical mechanism is unclear. The authors strongly suggest in this paper that the identification of the homogeneity of parent rocks of weathering crust in karst regions is of prime necessity.

Study on Microbes and Their Effects on Rare Earth Extraction in Weathering Crust of Granite

Microbes were cultured from the samples at various depths in a weathering profile of RE-bearing granite in Gonghe RE mine, Guangdong Province. The cultured microbes, existing at a depth of 0.2 similar to 12 in and being more plentiful within 3 in in the profile, include bacteria ( Bacillus, Enterobacter, Escherichia, Alkaligenes, Neisseria, Staphylococcus and anaerobic bacteria such as Clostridium), fungi ( Aspergillus niger, Aspergillus flavus, Penicillium, Mucor and Saccharomycete) and actinomyces. Experiments were made under room temperature by using solutions of the cultured microbes and their metabolites, compared with distilled water and the culture solution without microbes, to leach RE from the sample of the weathering crust. The results are shown by the experiments: (1) The mixed microbes cultured from the profile and their metabolites increase the quantity of RE leached from the sample and reduce the pH of the solutions. (2) The ability to leach RE from the sample varies with various microbes, decreasing in a sequence of fungi ( Mucor, saccharomycete, Aspegillus and Penicillium), zymotic bacilli (Enterobacter, Escherichia etc.), Staphylococcus, zymotic Bacillus, actinomyces and Alkaligenes. (3) The RE leached with bacteria is mainly related to the pH value of the solutions influenced by the metabolites of the bacteria; whereas that leached with fungi is mainly related to the adsorption and imbibition of RE by the fungi and the complexing of RE with their metabolites. (4) Compared with that leached with ammonium sulfate, the fractionation of the RE leached with microbes is characterized by higher delta (Ce), lower delta (Eu) and lower ratios of N-La/Sm and N-Gd/Yb . The result of the fractionation of RE accords with the distribution of RE in the various layers of a profile of weathering crust of granite in South China. The experimental results indicate that microbes and their metabolites should play a positive role in the mobilization, migration and fractionation of RE in the weathering crust in South China.

An Experimental Study on the Effects of Microbes on the Migration and Accumulation of REE in the Weathering Crust of Granite

Microbes were cultured and identified from the samples collected at various depths in 4 weathering profiles of REE\|bearing granites in Gonghe, Guangdong. The microbes were found existing at the depth of 0-5 m in all the profiles. The main microbes include coccus (Staphylococcus, Streptococcus), bacillus (Bacillus, Clostridium and Escherichia Coli), actinomyces and fungi (Saccharomycete, Penicillium, Fusarium, Aspergillus Aiger and Mucor). The number of colonies decreases downwards in the profiles. Experimental studies show that all the microbes used in the experiment can accelerate downward migration of REE in the experimental tubes. The ability to accelerate the migration of REE decreases in a sequence of fungi→actinomyces→bacillus→coccus. The microbes can change the modes of occurrence of REE in the weathering crust. The coccus, bacillus and actinomyces can increase the amounts of REE in ion state, whereas the fungi have a stronger ability to form organic compounding REE and accumulate REE than the bacteria do.

RED WEATHERING CRUST ON LIMESTONE AND PLANATION SURFACE OF TIBET AND ITS EASTERN DISTRICT

The fieldwork and experiments indicate that the red weathering crust, which developed on the limestone of Tibet Plateau and its eastern district, is a component of common planation surface of karst. The evidences are as follows: (1) They distributed in transverse continuity and often covered on the summit plane of hills. They correspond with a certain geomorphologic surface, for example, near Lijiang of Yunnan, there are summit planes of little undulation, the red weathering crust of large area distributed on the summit plane, and there are also many dolines and closed depressions up to hundreds of meters in diameter. (2) According to the situation of karst development, the soil loss made the fine sediments to be washed away through the crack in the district which vertical process developed well. Therefore, even if in the most active district of karst process, the weathering crust of continuous heavy layer can not be formed only if there existed a certain undulation. The organic soil and redizina can only be formed, and their main types of soil profile are AF\|D and A\|D. The thick weathering crust is only observed on the karst plane nearby base\|level of erosion. (3) The existence of terra rossa indicates the humid tropical/subtropical environment. The study results show that the component of red weathering crust on the limestone generally had the character of high content of clay particles(<2μm) and the weak process of silicon losing and aluminium concentration comparing with typical terra rossa. These characters indicate that its forming environment was humid and eluviation was weak. This situation only existed in the peneplain environment where groundwater was shallow and drainage condition was not very well. In a word, the forming time of thick weathering crust in the limestone district corresponded with the period of peneplain, and the forming altitude height was near the base level of erosion. So the red weathering crust of limestone had the significance of geomorphologic stage. These knowledges were important for assessing of the degree of Tibet Plateau uplift by the use of red weathering crust.

Compounding Pattern of REE， Clay and Humic Acid in the Weathering Crust of Granites

An anomalous phase containing clays and humic acid was found while extraction humic acid from samples of weathering crust of REE-bearing granites by using 0.1 mol/L NaOH solution.Studied by chemical separation experiments,column chromatography,ion-exchange chromatography,infrared spectrum.fluorescence spectrum,polarimicroscopic testing and elemental determination by ultraviolet-visible spectrometer and atomic absorption spectrometer.it was proved to be a compound of humic acid and clays which are connected in the form of bridge by heteronuclearpolynuclear complexing ions formed by cations of RE￣(5+),Al￣(3+).Fe￣(3+) etc.The compounding pattern was further proved by the experiment for compounding humic acid,REE and kaolinite.

Organic Metallogeny of Weathering Crust RE Deposit

A series of experimental geochemical studies have been done to confirm the organic metallogenic mechanism of weathering crust RE deposits. It has been concluded that: (1) Rich REbearing weathering crusts contain abundant organisms such as monoacids, diacids and nonacid compounds. Varieties and quantities of the organisms decrease from the upper to the lower of the profile. Humic acids are mainly fulvic acids, which are characterized by containing conjugated π system, carboxylic group, hydroxyl group and only a few nitrogenous groups. No obvious benzene ring has been found. (2) The upper part of the weathering crust contains a great deal of microorganisms, of which the varieties and quantities decrease from the upper to the lower of the profile. No microorganism has been found in the deep part of the profile. The microorganisms and their metabolites such as aminoacids, shortchain acids and organic compounds with small molecular weights can form water soluble RE complexes, which accelerate the RE transportation from original rocks and precipitation states to watersoluble states and thus provide prerequisites for retransportation and reaccumulation of RE. (3) Medium and longchain acids can form REnAm(OH)x(H2O)y type mixedligand polynuclear RE complexes, which devoted to the RE accumulation, whereas shortchain acids and aminoacids can form not only mixedligand complexes with RE, but also water soluble complex ions, which also devoted to the transport and accumulation of RE. (4) The fulvic acids are very soluble in water. They are apt to be mobile in the weathering crust and are able to form soluble complex ions and insoluble mixedligand polynuclear complexes with RE at normal temperature and atmospheric pressure and pH4～6. The composition of these complexes varies with different conditions of the weathering crust. (5) All the organic acids, fulvic acids and microorgaisms have contributed to keeping constant pH condition of the weathering crust. (6) Complexes consisting of clays, RE(Al, Fe……) and fulvic acids have been found in the weathering crust and a bonding pattern has been preliminarily studied. As a conclusion, the dissolution, transport and accumulaiton of REE during weathering is a organic and inorganic interacted process.

Fractionation characteristics of magnesium isotope in the ancient weathering crust

Weathering has always been a concerned around the world,as the first and most important step in the global cycle of elements,which leads to the fractionation of isotopes on the scale of geological age.The Middle Ordovician Majiagou Formation in Daniudi area of the Ordos Basin had experienced weathering for>130 Myr.Through thin section observation,major and trace element analysis,carbon,oxygen,and magnesium isotopes composition analysis,the dolomitization modes and weathering of ancient dolo-mite in Daniudi area were analyzed in detail.The results showed that the Sabkha and brine-reflux dolomitization modes had developed,and the Mg isotopes in different layers of the karst crust were fractionated by various factors.The vertical vadose zone was affected by weathering,the Mg isotope of dolomite(δ^(26)Mgdol)showed a downward decreasing trend;the horizontal underflow zone was controlled by diagenesis and formation fluid,δ^(26)Mgdol showed a vertical invariance and negative;the main reason for Mg isotope fractionation in the deep slow-flow zone was the brine-reflux dolomitization mode during early burial period,which showed a vertical downward increase.Finally,the Mg isotope characteristic data of the ancient weathering crust were provided and the process of Mg isotope frac-tionationinthekarstcrust was explained.

ON CHEMICAL WEATHERING OF WEATHERING CRUST AT THE GREAT WALL STATION REGION, ANTARCTICA

The chief aim of this study is to investigate the chemical weathering process of the weathering crust in Great Wall Station region of China (in Fildes Peninsula), Antarctica by the method of sedimentology.CW,SW,GW,TW,WE weathering crusts developed on volcanic clastic rock, gray aptitic basalt with tuff or basaltic bedrock. On change of minerals, geochemical behaviors of elements, migration and enrichment regularities of elements, Correlation between element geochemical behaviors, change of weathering potential of rocks in chemical weathering process are studied by us.We can see that the sequence fo weathering strengths of the abovementioned sections, from high to low, should reflected in TW, GW, CW and SWT and basical correspond with that calculated from the enrichment and differentiation indexes.

Experimental Study on the Effects of Organic Acids on the Dissolution of REE in the Weathering Crust of Granite

The results of REE leached by some organic acids with various concentrations and water/rock ratios for different durations from a mixed sample of the weathering crust of a granite in Gonghe, Guangdong, China, showed that: 1) the contents of REE leached increase with increasing concentrations of the organic acids; 2) the contents of REE leached by 0.01 mol/L organic acids increase with increasing water/rock ratio; 3) the interaction between the organic acids and the samples enhances the pH value of the medium and the contents of REE leached tend to increase with decreasing pH value; and 4) compared with those leached by ammonia sulfate, the REE leached by the organic acids are characterized by a weaker negative Ce anomaly, a stronger negative Eu anomaly, and lower (La/Sm)\-N and (Gd/Yb)\-N ratios, indicating that the organic acids have made contributions to the fractionation of REE in the weathering crust.

Characteristics and identification of weathering crust of Pennsylvanian volcanic rocks in Shixi area,Junggar Basin

Based on drill core and thin section observation,major geochemical element analysis and con-ventional well log analysis,this study summarizes the characteristics and thickness of weathering crust of Pennsylvanian volcanic rocks(Carboniferous)in Shixi area,Junggar Basin.The weathering crust is identified and divided into three types according to the petrological characteristics and well log interpretations in Shixi area,and the isopach of weathering crust is mapped.The results show that:(1)With the increase of depth,the weathering weakens,and the rocks become less fractured with decreased porosity;(2)the weathering crust of the Upper Carboniferous volcanic rocks can be divided into strongly weathered and mildly weathered layers in Shixi area;(3)the weathering crust is relatively thicker in Dinan uplift and Shixi uplift.This study provides research basis for further evaluation of Upper Carboniferous volcanic reservoir,and will benefit for well location deployment and potential oilfield development in the Shixi area.

Effects of cementation on physical properties of clastic rock-originated weathering crust reservoirs in the Kexia region,Junggar Basin,NW China

Cements are widely developed in clastic rock-originated weathering crust(CWC)reservoirs in the Kexia region along the northwestern margin of the Junggar Basin and significantly affect reservoir physical properties and oil and gas distribution in this area.Focusing on the CWC reservoirs at the top of both the Permian Jiamuhe Formation and the Triassic Karamay Formation,this study analyzed the types and characteristics of cements in the reservoirs and explored their effects on reservoir physical properties based on thin sections,SEM images,XRD results,and tests of physical properties.The main results are as follows.The cements in the CWC reservoirs in Kexia region mainly consist of carbonate minerals(41.5%),clay minerals(27.8%)and zeolite minerals(30%),as well as small amount of siliceous minerals.Among them,the carbonate minerals are dominated by siderite and calcite,the clay minerals mainly include kaolinite,interstratified illite/smectite(I/S)and chlorite,and the zeolite minerals primarily comprise heulandite and laumontite.These different types of multiphase cements are generally paragenetic or associated and affect reservoir physical properties to different degrees.Specifically,the carbonate and clay cements of the early diagenetic stage reduced the reservoirs’average porosity from 21%to 15%.The dissolution of some carbonate and zeolite cements in the early A substage of the middle diagenetic stage restored the average porosity to 18%,and the cementation in the late A substage decreased the average porosity to 13%again,of which about 4%was reduced by carbonate cements.The average porosity of the CWC reservoirs gradually decreased to the current value of approximately 10%in the B substage of the middle diagenetic stage.The impact of cementation on the CWC reservoirs can reach as far as 70 m below the unconformity.Moreover,the types and contents of cements vary with their depth below the unconformity surface,leading to the development of multiple zones with high cement content and the differentiated oil and gas distribution.

Column leaching process of rare earth and aluminum from weathered crust elution-deposited rare earth ore with ammonium salts

In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.

Leaching process of rare earths from weathered crust elution-deposited rare earth ore

In order to strengthen the leaching procedure,the chemical processes of leaching rare earths (RE) from the weathered crust elution-deposited rare earth ore were investigated frow the viewpoints of kinetics,hydrodynamic and mass transfer.The results show that the leaching hydrodynamics follows the Darcy law.The leaching kinetics can be described by the shrinking core model;the leaching process is controlled by diffusion of porous solid layer;and the mass transfer can be described with Van Deemter equation.This provides a theoretic basis and a scientific approach with high efficiency and optimized extraction conditions in industrial practice.

Correlation analysis on partition of rare earth in ion-exchangeable phase from weathered crust ores

The rare earth(RE)in weathered crust ores mainly exists as ion-exchangeable phase,approximately 80%.The correlation analysis on partition of 376 samples in ion-exchangeable phase from weathered crust ores was conducted.The results show that partition both among heavy RE elements and light RE elements with high partition appears positive correlation,but partition sums between the heavy RE elements and the light RE elements appear close negative correlation obviously.Clear negative correlations exist between the light RE elements(except Ce)and yttrium(Y).Matrix of correlation analysis on this partition can be divided into three zones.The correlated coefficient variation from negative to positive in zones B and C occurs at Gd,so does that in zones B and A(except Ce,Eu,and Sm),suggesting that RE elements can be divided into two groups with Gd as border.This phenomenon is called Gadolinium-broken effect.

Characteristics and Genetic Analysis of the Deep-buried Weathered-crust Karst Hydrocarbon Reservoirs of the Lower Paleozoic Group in the Tarim Basin

The genetic analysis of the deep-buried reservoirs of the Lower Paleozoiccarbonate rocks in the Tarim basin is a difficult task involving many factors. Firstly, the objectof study is carbonate rocks, which have undergone a long term of modification. Secondly, the rocksare deeply buried with depths of 3800-7000 m in the Tarim basin. The primary reservoir propertiesformed in the deposition have been strongly modified during the deep burial process. Concurrently,the different burial depths in different areas result in diversities of burial temperature,pressure, underground water, hydrochemistry and various physicochemical changes, which further leadto differences in the diagenetic type, diagenetic property, diagenetic degree and their impacts onthe reservoir properties. The Lower Paleozoic Cambrian and Ordovician carbonate reservoirs in theTarim basin can be grouped into four types, i.e., paleo-weathered-crust reservoirs, reef reservoirs,buried karst reservoirs and dolomite reservoirs. This paper presents a detailed discussion on thevertical and horizontal distribution characteristics, morphological division, reservoir propertiesand the efficiency in accumulating hydrocarbons of the paleo-weathered-crust type. Furthermore, itsgenesis is also analyzed. We proposed that the composition of the carbonate rocks, the tectonicmovement with associated fractures and fissures, the paleomorphology and paleoclimate, the sea levelfluctuation, and the protection of the pores and fissures by the deep burial diagenesis and burialdissolution are the main factors controlling the formation of the paleo-weathered-crust reservoirs.We also consider that the petroleum exploration of the Lower Paleozoic carbonate rocks should befocused on the pale-weathered-crust reservoirs.