Contrasting sources and enrichment mechanisms in lithium-rich salt lakes:A Li-H-O isotopic and geochemical study from northern Tibetan Plateau

Lithium(Li),a crucial mineral resource for modern high-tech industries,is notably abundant in the northern Tibetan Plateau,primarily within lithium-rich salt lakes.However,the exploration and development of these resources are hindered due to an incomplete understanding of their nature and origin.Here we present results from a comprehensive study on the hydrochemical parameters,whole-rock geochemistry,H-O isotopes,and Li concentrations in surface brine,river water,geothermal springs,and associated rocks from two representative lithium-enriched salt lakes,the Laguo Co(LGC)and Cangmu Co(CMC)in Tibet to understand the genetic mechanisms.Our water-salt balance calculations and H-O isotopic analysis reveal that Li in LGC and CMC primarily originates from the Suomei Zangbo(SMZB,~91%)and Donglong Zangbo(DLZB,~75%)rivers,respectively.It is estimated that the LGC and CMC took a minimum of 6.0 ka and 3.0 ka to accumulate their current lithium resources,respectively.The distinct geological characteristics reflect evolutionary differences between the two lakes,suggesting diverse lithium sources and enrichment processes.The high lithium ion concentration and light lithium isotope composition in the SMZB river waters indicate the genetic relationship with lithium-enriched geothermal springs in the Tibetan Plateau.Our results suggest that lithium in the LGC originates from lithium-enriched geothermal springs and is primarily supplied through the small-scale SMZB river.In contrast,the formation and evolution of CMC are influenced by the northern Lunggar rifts,receiving a prolonged and stable input from the DLZB,resulting in high lithium concentrations and isotopic values.The absence of lithium-enriched geothermal springs and the prevalence of silicate rocks in the CMC catchment suggest that lithium may be sourced from the weathering of silicate rocks,such as granitic pegmatite veins containing lithium-rich beryl,widely distributed in the upstream area of DLZB.The forward modeling approach,quantifying the contribution fractions of different reservoirs(atmospheric precipitation,silicate,carbonate,and evaporite),indicates that the distinct lithium concentrations in the mainstream(>1 mg/L)and tributaries(<0.1 mg/L)are positively correlated with the ratio of silicate contributions to carbonate contributions,suggesting that dissolved lithium in river waters primarily originates from the weathering and dissolution of silicate rocks.The distinct sources and enrichment mechanisms of lithium in these two salt lakes are attributed to various evolutionary processes,topographical features,hydrological factors,fundamental geological settings,and tectonic histories,despite their spatial proximity.Furthermore,our study highlights the significant role of rivers in the formation of young salt lakes,in addition to geothermal springs.

Paleoenvironment evolution and organic matter enrichment mechanisms in the first member of the Qingshankou Formation,Songliao Basin,China

Organic matter is the basis for oil and gas generation,and the depositional environment controls its enrichment.The first member of the Qingshankou Formation(K_(2)qn^(1))in Songliao Basin has a thick organic-rich shale and so is an important target section for shale oil exploration and development.In the Gulong Sag,shale samples from this unit were collected over the full length of the section.The characterization of the environments of deposition(EOD)of K_(2)qn^(1)was improved by utilizing lithological characteristics,thin section observations,elemental compositions,and organic carbon concentrations.Combined with the normalization coefficients proposed in this paper,an organic matter correlation model was established to elucidate the factors that influence organic matter enrichment.From the bottom to the top of K2qn1,the lake depth gradually becomes shallower,the primary productivity first decreases and then increases,the reducing conditions become stronger and then weaker,the water salinity gradually decreases,the climate first becomes semi-humid and then warm and humid,and the input of terrigenous debris first decreases and then increases.A major marine transgression at the base of the K_(2)qn^(1)᾽s brought in nutrients to increase primary productivity,and the density-stratified reducing environment preserved and enriched organic matter.High primary productivity occurred during the middle of the deposition of the K_(2)qn^(1),while terrigenous input is low.Organic matter is preserved in reduced deep lake environments,resulting in organic matter-rich black shale.The lake became shallower,and the salinity decreased in the upper part of K_(2)qn^(1).Benthic organisms rapidly multiplied,consuming large amounts of oxygen and destroying the previously depositional environment,resulting in a reducing environment disturbed by benthic organisms with poor preservation conditions and the lowest organic matter content.

The occurrence phases and enrichment mechanism of rare earth elements in cobalt-rich crusts from Marcus-Wake Seamounts

To explore the occurrence phases and enrichment mechanism of rare earth elements(REEs)in cobalt-rich crusts,this study analyzes the mineral composition and REE contents of the samples from Marcus-Wake Seamounts by XRD,ICP-OES and ICP-MS.The results show that,(1)the cobalt-rich crusts contain the major crystalline mineral(vernadite),the secondary minerals(quartz,plagioclase and carbonate fluorapatite),and a large amount of amorphous ferric oxyhydroxides(FeOOH).(2)The cobalt-rich crusts contains higher Mn(10.83%to 28.76%)and Fe(6.14%to 18.86%)relative to other elements,and are enriched in REEs,with total REE contents of 1563−3238μg/g and Ce contents of 790−1722μg/g.Rare earth element contents of the old crusts are higher than those of the new crusts.Moreover,the non-phosphatized crusts have positive Ce and negative Y anomalies,and yet the phosphatized crusts have positive Ce and positive Y anomalies,indicating that cobalt-rich crusts is hydrogenetic and REEs mainly come from seawater.(3)Analytical data also show that the occurrence phases of elements in cobalt-rich crusts are closely related to their mineral phases.In the non-phosphatized crusts,REEs are adsorbed by colloidal particles into the crusts(about 67%of REEs in the Fe oxide phase,and about 17%of REEs in the Mn oxide phase).In contrast,in the phosphatized crusts(affected by the phosphatization),REEs may combine with phosphate to form rare earth phosphate minerals,and about 64%of REEs are enriched in the residual phase containing carbonate fluorapatite,but correspondingly the influence of Fe and Mn oxide phases on REEs enrichment is greatly reduced.In addition,the oxidizing environment of seawater,high marine productivity,phosphatization,and slow growth rate can promote the REE enrichment.This study provides a reference for the metallogenesis of cobalt-rich crusts in the Pacific.

Differences in and factors controlling organic matter enrichment in the Ziliujing Formation shale in the Sichuan Basin

Lacustrine shale oil and gas are important fields for unconventional exploration and development in China,and organic-rich shale deposition lays down the critical foundation for hydrocarbon generation.There are two sets of shale,the Dongyuemiao and Da’anzhai Members,in the Ziliujing Formation in the Sichuan Basin.To identify the differential enrichment characteristics of organic matter and clarify its controlling factors,geochemical analyses of organic and inorganic geochemical analyses were performed.The results showed that the total organic carbon content of the Dongyuemiao shale(1.36%)is slightly higher than that of the Da’anzhai shale(0.95%).The enrichment of organic matter in the two shales resulted from the comprehensive controls of paleoproductivity,paleoenvironment,and terrigenous input,but different factors have different effects.In addition,driven by climate,the change in the sulfate concentration in the bottom water further led to the different intensities of bacterial sulfate reduction in early diagenesis.This made a great difference regarding organic matter accumulation in the two members.In general,climate may have played a dominant role in organic matter enrichment in the two sets of shale.

Enrichment Mechanism and Prospects of Deep Oil and Gas

With the deepening of oil and gas exploration,the importance of depth is increasingly highlighted.The risk of preservation of storage space in deep reservoirs is greater than that in shallow and medium layers.Deep layers mean older strata,more complex structural evolution and more complex hydrocarbon accumulation processes,and even adjustment and transformation of oil and gas reservoirs.This paper systematically investigates the current status and research progress of deep oil and gas exploration around the world and looks forward to the future research focus of deep oil and gas.In the deep,especially the ultra-deep layers,carbonate reservoirs play a more important role than clastic rocks.Karst,fault-karst and dolomite reservoirs are the main types of deep and ultra-deep reservoirs.The common feature of most deep large and medium-sized oil and gas reservoirs is that they formed in the early with shallow depth.Fault activity and evolution of trap highs are the main ways to cause physical adjustment of oil and gas reservoirs.Crude oil cracking and thermochemical sulfate reduction(TSR)are the main chemical modification effects in the reservoir.Large-scale high-quality dolomite reservoirs is the main direction of deep oil and gas exploration.Accurate identification of oil and gas charging,adjustment and reformation processes is the key to understanding deep oil and gas distribution.High-precision detection technology and high-precision dating technology are an important guarantee for deep oil and gas research.

Enrichment of tight oil and its controlling factors in central and western China

Taking the tight oil of the Zhongnan sag in the Ordos Basin,Jimusar sag in the Junggar Basin and Qingxi sag in the Jiuquan Basin as study objects,based on field survey,dissection of tight oil reservoirs,sample test,modeling experiment and comprehensive analysis,this study reveals that the tight oil accumulates at start-up pressure,advances under differential pressure,diffuses at alternating fast and low speeds,charges in stepped large area and migrates rapidly through fractures,and enriches in dominant fractures and pores.The root cause of ladder-like charge is the multiple scales of pores.The widespread source rock with high hydrocarbon generation intensity is the material basis for tight oil enrichment;the dominant source reservoir assemblage is the basic unit for tight oil enrichment;fractures and beddings are conducive to local rapid migration of tight oil;fractures and pores work together to control the enrichment of tight oil.Two typical accumulation models of tight oil are established,namely"source reservoir in coexistence,four optimal factors controlling enrichment around central area,and large-scale continuous distribution"for a large freshwater lake clastic rock basin and"source reservoir integration,four optimal factors controlling enrichment,central area distribution,small in size but high in enrichment degree"for a small saline lake diamictite depression.

Sedimentary facies characteristics and organic matter enrichment mechanism of lower Cambrian Niutitang Formation in South China

The purpose of this study was to examine the sedimentary facies characteristics of lower Cambrian Niutitang Formation(∈1n)in South China,to reveal the mechanism of organic matter enrichment,and to guide exploration of shale gas.Macro investigation and experimental analyses were used to assess the lithology in detail,total organic matter mass fraction w(TOC),mineral composition,and trace element characteristics of∈1n.The influencing factors of organic matter enrichment were discussed extensively,and a sedimentary facies mode was suggested.In the early stage of∈1n,the locations of Well E’yangye 1,Well Ciye 1,Well Changye 1,and Well Anye 1 respectively develop,platform inner sag,outer shelf,Jiangnan slope belt,and South China detention basin.In the late stage of∈1n,the sedimentary facies evolve with decreasing sea level.The study area presents a complete three-step basin in the Early Cambrian.In the early stage of∈1n,the first step is the Yangtze carbonate platform,the second step is the outer shelf and slope,and the third step is the deep-water basin.From the Yangtze carbonate platform to the deep-water basin,w(TOC)and the mass fraction of quartz gradually increase,the mass fraction of carbonate mineral decreases,and the mass fraction of clay mineral is higher in the second step.The sea level fluctuation results in a higher w(TOC)vertically in the lower∈1n shale,and the paleogeographic(provenance)conditions lead to better horizontal development of organic matter in the outer shelf,slope and detention basin.Trace elements are abundant in the lower∈1n,and w(TOC)is correlated positively with many trace elements.In the outer shelf,slope,and adjacent areas,hydrothermal activity and upwelling current bring nutrient-rich material and promote organic matter enrichment under a strong reducing condition.Deep-shelf,slope and deep-water basin are the best facies for the formation and preservation of organic matter,especially deep-water basin facies.It remains necessary to strengthen the exploration of shale gas in the deep-water basin of∈1n in central Hunan,China.

Source,migration,distribution,toxicological effects and remediation technologies of arsenic in groundwater in China

Groundwater with high arsenic(As) content seriously threatens human life and health. Drinking high-As groundwater for a long time will lead to various pathological changes such as skin cancer, liver cancer,and kidney cancer. High-As groundwater has become one of the most serious environmental geological problems in China and even internationally. This paper aims to systematically summarize the sources,migration, distribution, toxicological effects, and treatment techniques of As in natural groundwater in China based on a large number of literature surveys. High-As groundwater in China is mainly distributed in the inland basins in arid and semi-arid environments and the alluvial and lacustrine aquifers in river deltas in humid environments, which are in neutral to weakly alkaline and strongly reducing environments.The content of As in groundwater varies widely, and As(Ⅲ) is the main form. The main mechanism of the formation of high-As groundwater in China is the reduced dissolution of Fe and Mn oxides under the action of organic matter and primary microorganisms, alkaline environment, intense evaporation and concentration, long-term water-rock interaction, and slow groundwater velocity, which promote the continuous migration and enrichment of As in groundwater. There are obvious differences in the toxicity of different forms of As. The toxic of As(Ⅲ) is far more than As(V), which is considered to be more toxic than methyl arsenate(MMA) and dimethyl arsenate(DMA). Inorganic As entering the body is metabolized through a combination of methylation(detoxification) and reduction(activation) and catalyzed by a series of methyltransferases and reductases. At present, remediation methods for high-As groundwater mainly include ion exchange technology, membrane filtration technology, biological treatment technology, nanocomposite adsorption technology, electrochemical technology, and so on. All the above remediation methods still have certain limitations, and it is urgent to develop treatment materials and technical means with stronger As removal performance and sustainability. With the joint efforts of scientists and governments of various countries in the future, this worldwide problem of drinking-water As poisoning will be solved as soon as possible. This paper systematically summarizes and discusses the hot research results of natural high-As groundwater, which could provide a reference for the related research of high-As groundwater in China and even the world.

Hydrocarbon Generation Potential and Organic Matter Enrichment Mechanism of the Cambrian Marine Shale in the Tadong Low Uplift,Tarim Basin

Cambrian shales in China and elsewhere contain abundant oil and gas resources.However,due to its deep burial and limited outcrop,there has been relatively little research conducted on it.The Cambrian shale of the Tadong low uplift in the Tarim Basin of western China,specifically the Xidashan-Xishanbulake Formation(Fm.)and overlying Moheershan Fm.provide a case study through the use of organic petrology,mineralogy,organic and elemental geochemistry,with the aim of analyzing and exploring the hydrocarbon generation potential(PG)and organic matter(OM)enrichment mechanisms within these shale formations.The results indicate that:(1)the Cambrian shale of the Tadong low uplift exhibits relatively dispersed OM that consists of vitrinite-like macerals and solid bitumen.These formations have a higher content of quartz and are primarily composed of silica-based lithology;(2)shale samples from the Xidashan-Xishanbulake and Moheershan formations demonstrate high total organic carbon(TOC)and low pyrolytic hydrocarbon content(S_(2))content.The OM is predominantly typeⅠand typeⅡkerogens,indicating a high level of maturation in the wet gas period.These shales have undergone extensive hydrocarbon generation,showing characteristics of relatively poor PG;(3)the sedimentary environments of the Xidashan-Xishanbulake and Moheershan formations in the Tadong low uplift are similar.They were deposited in warm and humid climatic conditions,in oxygen-deficient environments,with stable terrigenous inputs,high paleoproductivity,high paleosalinity,weak water-holding capacity,and no significant hydrothermal activity;and(4)the relationship between TOC and the paleoproductivity parameter(P/Ti)is most significant in the Lower Cambrian Xidashan-Xishanbulake Fm.,whereas correlation with other indicators is not evident.This suggests a productivity-driven OM enrichment model,where input of landderived material was relatively small during the Middle Cambrian,and the ancient water exhibited lower salinity.A comprehensive pattern was formed under the combined control of paleoproductivity and preservation conditions.This study provides valuable guidance for oil and gas exploration in the Tarim Basin.

Rare earth elements-rich phase and enriching mechanism in sediments from CC area, the Pacific Ocean

Compared to North American shale composition (NASC), REE contents of sediments from the CC area in the Pacific Ocean are obviously high except that cerium has equal content to that of NASC. Three-valence rare earth elements were completely enriched in phosphate-phase and cerium in iron-phase. Rare earth elements in the sediments were originally derived from seawater. During lithi- genic and minerogenic processes of metalliferous nodules, three-valence rare earth elements in sediments mobilized and incorporated into sediments as authigenous biogenic-apatite, while cerium had change from Ce3+ to Ce4+ and directly precipitated from seawater and entered metalliferous nodules and caused Ce anomalies in REE pattern in sediments.

Enrichment mechanism and resource potential of shale-type helium:A case study of Wufeng Formation-Longmaxi Formation in Sichuan Basin

China’s helium resource is highly dependent on overseas imports.Organic-rich and U/Th-rich shale reservoirs generally contain helium,and although the helium content is low,the total reserve is large.Therefore,the effective development and utilisation of shale-type helium resources is a realistic way to improve the security of helium resources in China.In this study,the generation mechanism,helium source and content,migration modes and pathways,controlling factors of enrichment,distribution pattern,and resource potential of the helium were analysed,using the Wufeng-Longmaxi shale in the Sichuan Basin and its periphery.Furthermore,countermeasures were proposed for shale-type helium exploration and development.The results show that the Wufeng-Longmaxi shale has a high content of U and Th and a good ability to generate helium.The helium is generated by a typical crustal source of helium and is characterised by self-generation,self-storage,and wide distribution.The helium resource potential is a product of its content and the resources of the associated natural gas.The continuous supply of helium and effective preservation are the main geological factors that control the enrichment of shale-type helium.The preliminary evaluation results show that the reserves of helium in proven shale gas reserves are 10.8×10^(8)m^(3)in the Sichuan Basin and its periphery,where the extra-large helium fields are likely to be discovered.Additionally,0.0912×10^(8)m^(3)of helium was produced,along with the annual production of shale gas.To avoid the waste of helium and to improve the self-supply ability,it is suggested that research on the resource potential,enrichment mechanism,and distribution pattern of shale-type helium should be carried out as soon as possible,and helium extraction techniques for helium-bearing natural gas should be studied.

Distribution,enrichment mechanism and risk assessment for fluoride in groundwater:a case study of Mihe-Weihe River Basin,China

Due to the unclear distribution characteristics and causes of fluoride in groundwater of Mihe-Weihe River Basin(China),there is a higher risk for the future development and utilization of groundwater.Therefore,based on the systematic sampling and analysis,the distribution features and enrichment mechanism for fluoride in groundwater were studied by the graphic method,hydrogeochemical modeling,the proportionality factor between conventional ions and factor analysis.The results show that the fluorine content in groundwater is generally on the high side,with a large area of medium-fluorine water(0.5–1.0 mg/L),and high-fluorine water is chiefly in the interfluvial lowlands and alluvial-marine plain,which mainly contains HCO_(3)·Cl-Na-and HCO_(3)^(-)Na-type water.The vertical zonation characteristics of the fluorine content decrease with increasing depth to the water table.The high flouride groundwater during the wet season is chiefly controlled by the weathering and dissolution of fluorine-containing minerals,as well as the influence of rock weathering,evaporation and concentration.The weak alkaline environment that is rich in sodium and poor in calcium during the dry season is the main reason for the enrichment of fluorine.Finally,an integrated assessment model is established using rough set theory and an improved matter element extension model,and the level of groundwater pollution caused by fluoride in the Mihe-Weihe River Basin during the wet and dry seasons in the Shandong Peninsula is defined to show the necessity for local management measures to reduce the potential risks caused by groundwater quality.