Efficient and rapid capture of uranium(Ⅵ) in wastewater via multiamine modified β-cyclodextrin porous polymer

It is quite important to ensure the safety and sustainable development of nuclear energy for the treatment of radioactive wastewater. To treat radioactive wastewater efficiently and rapidly, two multi-amine β-cyclodextrin polymers(diethylenetriamine β-cyclodextrin polymer(DETA-TFCDP) and triethylenetetramine β-cyclodextrin polymer(TETA-TFCDP)) were prepared and applied to capture uranium. Results exhibited that DETA-TFCDP and TETA-TFCDP displayed the advantages of high adsorption amounts(612.2and 628.2 mg·g-1, respectively) and rapid adsorption rates, which can reach(88 ± 1)% of their equilibrium adsorption amounts in 10 min. Moreover, the adsorbent processes of DETA-TFCDP and TETATFCDP on uranium(Ⅵ) followed the Langmuir model and pseudo-second-order model, stating they were mainly chemisorption and self-endothermic. Besides, TETA-TFCDP also showed excellent selectivity in the presence of seven competing cations and could be effectively reused five times via Na2CO3as the desorption reagent. Meanwhile, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy illustrated that the enriched multi-amine groups and oxygen-containing functional groups on the surface of TETA-TFCDP were the main active sites for capturing uranium(Ⅵ). Hence, multi-amine β-cyclodextrin polymers are a highly efficient, rapid, and promising adsorbent for capturing uranium(Ⅵ)from radioactive wastewater.

Apatite Fission Track Thermochronology of Granite from the Xiazhuang Uranium Ore Field,South China:Implications for Exhumation History and Ore Preservation

Xiazhuang uranium ore field,located in the southern part of the Nanling Metallogenic Belt,is considered one of the largest granite-related U regions in South China.In this paper,we contribute new apatite fission track data and thermal history modeling to constrain the exhumation history and evaluate preservation potential of the Xiazhuang Uranium ore field.Nine Triassic outcrop granite samples collected from different locations of Xiazhuang Uranium ore field yield AFT ages ranging from 43 to 24 Ma with similar mean confined fission track lengths ranging from 11.8±2.0 to 12.9±1.9μm and Dpar values between 1.01 and 1.51μm.The robustness time-temperature reconstructions of samples from the hanging wall of Huangpi fault show that the Xiazhuang Uranium ore field experienced a time of monotonous and slow cooling starting from middle Paleocene to middle Miocene(~60-10 Ma),followed by relatively rapid exhumation in the late Miocene(~10-5 Ma)and nearly thermal stability in the Pliocene-Quaternary(~5-0 Ma).The amount of exhumation after U mineralization since the Middle Paleogene was estimated as~4.3±1.8 km according to the integrated thermal history model.Previous studies indicate that the ore-forming ages of U deposits in the Xiazhuang ore field are mainly before Middle Paleocene and the mineralization depths are more than 4.4±1.2 km.Therefore,the exhumation history since middle Paleocene plays important roles in the preservation of the Xiazhuang Uranium ore field.

Bio-leaching effects of Leptospirillum ferriphilum on the surface chemical properties of pyrite

Leptospirillum ferriphilum cultured using different energy sources(either soluble ferrous ion or pyrite) changed the surface properties of pyrite.Cell adsorption,zeta-potential,hydrophobicty,FT-IR spectra and surface morphology were investigated.Adhesion of bacterial cells to the pyrite surface is a fast process.Furthermore,the adsorption of cells grown in pyrite is greater than of cells grown in soluble ferrous ion.The Iso-Electric Point(IEP) of pyrite treated with L.ferriphilum approaches that of the cells themselves.The contact angle of the pyrite surface was observed to decrease due to the surface formation of some hydrophilic substances during bio-leaching.Changes in pyrite surface properties after bacterial treatment support the idea that ferric ion plays an important role and that indirect bio-oxidation is the principal mechanism of pyrite bio-leaching.

Efficient and selective extraction of uranium from seawater based on a novel pulsed liquid chromatography radionuclide separation method

The novel pulsed liquid chromatography radionuclide separation method presented here provides a new and promising strategy for the extraction of uranium from seawater.In this study,a new chromatographic separation method was proposed,and a pulsed nuclide automated separation device was developed,alongside a new chromatographic column.The length of this chromatographic column was 10 m,with an internal warp of 3 mm and a packing size of 1 mm,while the total separation units of the column reached 12,250.The most favorable conditions for the separation of nuclides were then obtained through optimizing the separation conditions of the device:Sample pH in the column=2,sample injection flow rate=5.698 mL/min,chromatographic column heating temperature=60℃.Separation experiments were also carried out for uranium,europium,and sodium ions in mixed solutions;uranium and sodium ions in water samples from the Ganjiang River;and uranium,sodium,and magnesium ions from seawater samples.The separation factors between the different nuclei were then calculated based on the experimental data,and a formula for the separation level was derived.The experimental results showed that the separation factor in the mixed solution of uranium and europium(1:1)was 1.088,while achieving the initial separation of uranium and europium theoretically required a 47-stage separation.Considering the separation factor of 1.50for the uranium and sodium ions in water samples from the Ganjiang River,achieving the initial separation of uranium and sodium ions would have theoretically required at least a 21-stage separation.Furthermore,for the seawater sample separation experiments,the separation factor of uranium and sodium ions was 1.2885;therefore,more than 28 stages of sample separation would be required to achieve uranium extraction from seawater.The novel pulsed liquid chromatography method proposed in this study was innovative in terms of uranium separation and enrichment,while expanding the possibilities of extracting uranium from seawater through chromatography.

Branched fibrous amidoxime adsorbent with ultrafast adsorption rate and high amidoxime utilization for uranium extraction from seawater

Direct collection of uranium from low uranium systems via adsorption remains challenging.Fibrous sorbent materials with amidoxime(AO)groups are promising adsorbents for uranium extraction from seawater.However,low AO adsorption group utilization remains an issue.We herein fabricated a branched structure containing AO groups on polypropylene/polyethylene spun-laced nonwoven(PP/PE SNW)fibers using grafting polymerization induced by radiation(RIGP)to improve AO utilization.The chemical structures,thermal properties,and surface morphologies of the raw and treated PP/PE SNW fibers were studied.The results show that an adsorptive functional layer with a branching structure was successfully anchored to the fiber surface.The adsorption properties were investigated using batch adsorption experiments in simulated seawater with an initial uranium concentration of 500μg·L^(−1)(pH 4,25℃).The maximum adsorption capacity of the adsorbent material was 137.3 mg·g^(−1)within 24 h;moreover,the uranyl removal reached 96%within 240 min.The adsorbent had an AO utilization rate of 1/3.5 and was stable over a pH range of 4–10,with good selectivity and reusability,demonstrating its potential for seawater uranium extraction.

Depleted uranium oxide supported nickel catalyst for autothermal CO_(2)methanation in non-adiabatic reactor under induction heating

Undoped nickel-based catalysts supported on depleted uranium oxide allow one to carry out CO_(2)methanation process under extremely low reaction temperature under atmospheric pressure and powered by a contactless induction heating.By adjusting the reaction conditions,the catalyst is able to perform CO_(2)methanation reaction under autothermal process operated inside a non-adiabatic reactor,without any external energy supply.Such autothermal process is possible thanks to the high apparent density of the UO_x which allows one to confine the reaction heat in a small catalyst volume in order to confine the exothermicity of the reaction inside the catalyst and to operate the reaction at equilibrium heat in-heat out.Such autothermal operation mode allows one to significantly reduce the complexity of the process compared to that operated using adiabatic reactor,where complete insulation is required to prevent heat disequilibrium,in order to reduce as much as possible,the heat exchange with the external medium.The catalyst displays an extremely high stability as a function of time on stream as no apparent deactivation.It is expected that such new catalyst with unprecedented catalytic performance could open new era in the field of heterogeneous catalysis where traditional supports show their limitations to operate catalytic processes under severe reaction conditions.

Effect of Natural Zeolite on Pore Structure of Cemented Uranium Tailings Backfill

The use of some environmental functional minerals as backfill-modified materials may improve the leaching resistance of cemented uranium tailings backfill created from alkali-activated slag(CUTB),but these materials may participate in the hydration reaction of the cementitious materials,which could have a certain impact on the pore structure of the CUTB,thus affecting its mechanical properties and leaching resistance.In this paper,natural zeolite is selected as the backfill-modified material,and it is added to alkali-activated slag paste(AASP)and CUTB in cementitious material proportions of 4%,8%,12%,and 16%to prepare AASP mixtures and CUTB mixtures containing environmental functional minerals.After the addition of natural zeolite,the porosity of the CUTB generally increases,but when the content is 4%,the porosity decreases to 22.30%.The uniaxial compressive strength(UCS)of the CUTB generally decreases,but the decrease is the smallest when the content is 4%,and the UCS is 12.37 MPa.The addition of natural zeolite mainly reduces the number of fine pores in the CUTB,but the pores with relaxation times T_(2)of greater than 10 ms account for about 10%of the total pores,and there are a certain number of large pores in the CUTB.The main product of alkali-activated slag is calcium(alumino)silicate hydrate(C-(A)-S-H gel).When natural zeolite is added,the hydration products develop towards denser products with a high degree of polymerization and the formation of low polymerization products is reduced.This affects the internal fracture pores of the hydration products and the interface pores of the CUTB,has an irregular effect on the pore characteristics of the CUTB,and influences the UCS.

An artificial neural network potential for uranium metal at low pressures

Based on machine learning,the high-dimensional fitting of potential energy surfaces under the framework of first principles provides density-functional accuracy of atomic interaction potential for high-precision and large-scale simulation of alloy materials.In this paper,we obtained the high-dimensional neural network(NN)potential function of uranium metal by training a large amount of first-principles calculated data.The lattice constants of uranium metal with different crystal structures,the elastic constants,and the anisotropy of lattice expansion of alpha-uranium obtained based on this potential function are highly consistent with first-principles calculation or experimental data.In addition,the calculated formation energy of vacancies in alpha-and beta-uranium also matches the first-principles calculation.The calculated site of the most stable self-interstitial and its formation energy is in good agreement with the findings from density functional theory(DFT)calculations.These results show that our potential function can be used for further large-scale molecular dynamics simulation studies of uranium metal at low pressures,and provides the basis for further construction of potential model suitable for a wide range of pressures.

Application of sequential extraction for analyzing source and sink of uranium in Huanghe River sediments,China

Geochemical behaviors of heavy metals are closely related to their chemical state that can be divided by sequential extraction into exchangeable(F1),bound to carbonates(F2),bound to Fe-Mn oxides(F3),bound to organic matter or sulfide(F4),and residual(F5).Uranium in sediment of the Huanghe(Yellow)River,China,in different chemical states was extracted using the five-step procedure of Tessier and the source and sink were analyzed.Results show that more than 70%of the total uranium was immobile residual F5 in abundance,followed in order of F4>F3>F2>F1,indicating that the main source of uranium in the sediments was from weathered rock in the drainage basin.In addition,the uranium in the sediments presents potential exogenous input in the Lanzhou,Baotou,and Tongguan reach.Fe-Mn oxides are main carriers of unstable uranium,especially those of F1 and F3.Calcite and illite are secondary adsorption minerals of unstable uranium in sediments under natural conditions.Human activities can also produce an obvious impact on uranium speciation.This study provides a reference for the application of sequential extraction in analyzing the source and sink of uranium in river sediments.

Site selective 5f electronic correlations inβ-uranium

We investigate the electronic structure ofβ-uranium,which has five nonequivalent atomic sites in its unit cell,by means of the density functional theory plus Hubbard-U correction with U from linear response calculation.It is found that the 5f electronic correlations inβ-uranium are moderate.More interestingly,their strengths are site selective,depending on the local atomic environment of the present uranium atom.As a consequence,the occupation matrices and partial 5f density of states ofβ-uranium manifest site dependence.In addition,the complicate experimental structure ofβ-uranium could be well reproduced within this theoretical framework.

Assessment of Modeling Collimator Designs for Gamma-Ray Transmission of Uranium Oxide Spectrometry Using HPGe Detectors

Many scientific domains use gamma-ray spectrometry, but non-destructive gamma scanning and gamma emission tomography of radioactive fuel in particular. In the experimental setting, a collimator is frequently employed to focus on a particular location of interest in the fuel. Predictive models for the transmitted gamma-ray intensity through the collimator are required for both the optimization of instrument design and the planning of measurement campaigns. Gamma-ray transport accuracy is frequently predicted using Monte Carlo radiation transport methods, but using these tools in low-efficiency experimental setups is challenging due to the lengthy computation times needed. This study focused on the full-energy peak intensity that was transmitted through several collimator designs, including rectangle and cylinder. The rate of photons arriving at a detector on the other side of the collimator was calculated for anisotropic source of SNM (U3O8). Some geometrical assumptions that depended on the source-to-collimator distance and collimator dimensions (length, radius or length, height, and width) were applied to achieve precise findings.

Permeability evolution mechanism and the optimum permeability determination of uranium leaching from low-permeability sandstone treated with low-frequency vibration

Low-frequency vibrations can effectively improve natural sandstone permeability,and higher vibration frequency is associated with larger permeability.However,the optimum permeability and permeability evolution mechanism for uranium leaching and the relationship between permeability and the change of chemical reactive rate affecting uranium leaching have not been determined.To solve the above problems,in this study,identical homogeneous sandstone samples were selected to simulate lowpermeability sandstone;a permeability evolution model considering the combined action of vibration stress,pore water pressure,water flow impact force,and chemical erosion was established;and vibration leaching experiments were performed to test the model accuracy.Both the permeability and chemical reactions were found to simultaneously restrict U6þleaching,and the vibration treatment increased the permeability,causing the U6þleaching reaction to no longer be diffusion-constrained but to be primarily controlled by the reaction rate.Changes of the model calculation parameters were further analyzed to determine the permeability evolution mechanism under the influence of vibration and chemical erosion,to prove the correctness of the mechanism according to the experimental results,and to develop a new method for determining the optimum permeability in uranium leaching.The uranium leaching was found to primarily follow a process consisting of(1)a permeability control stage,(2)achieving the optimum permeability,(3)a chemical reactive rate control stage,and(4)a channel flow stage.The resolution of these problems is of great significance for facilitating the application and promotion of lowfrequency vibration in the CO_(2)+O_(2) leaching process.

Assessment of the Greenhouse Gas Footprint and Environmental Impact of CO_(2)and O_(2)in situ Uranium Leaching

Under the new development philosophy of carbon peaking and carbon neutrality,CO_(2)and O_(2)in situ leaching(ISL)has been identified as a promising technique for uranium mining in China,not only because it solves carbon dioxide utilization and sequestration,but it also alleviates the environmental burden.However,significant challenges exist in assessment of CO_(2)footprint and water-rock interactions,due to complex geochemical processes.Herein this study conducts a three-dimensional,multicomponent reactive transport model(RTM)of a field-scale CO_(2)and O_(2)ISL process at a typical sandstone-hosted uranium deposit in Songliao Basin,China.Numerical simulations are performed to provide new insight into quantitative interpretation of the greenhouse gas(CO_(2))footprint and environmental impact(SO_(4)^(2–))of the CO_(2)and O_(2)ISL,considering the potential chemical reaction network for uranium recovery at the field scale.RTM results demonstrate that the fate of the CO_(2)could be summarized as injected CO_(2)dissolution,dissolved CO_(2)mineralization and storage of CO_(2)as a gas phase during the CO_(2)and O_(2)ISL process.Furthermore,compared to acid ISL,CO_(2)and O_(2)ISL has a potentially smaller environmental footprint,with 20%of SO_(4)^(2–)concentration in the aquifer.The findings improve our fundamental understanding of carbon utilization in a long-term CO_(2)and O_(2)ISL system and provide important environmental implications when considering complex geochemical processes.

渗出砂岩型铀矿成矿预测与找矿标志

文章基于渗出砂岩型铀矿成矿机理和模式,认为渗出砂岩型铀成矿作用不同于渗入砂岩型铀矿成矿作用,其成矿预测和找矿标志也不同;提出了渗出砂岩型铀矿成矿作用两大基本关键条件识别标志:红杂色含矿建造原生成因和其中控矿灰色砂体的后生成因识别;在提出的红杂色沉积建造中渗出砂岩型铀矿“上红下黑、上下连通、红中找灰、灰中找矿”总体找矿新思路基础上,阐明渗出砂岩型铀成矿区域预测评价条件和标志:深部富铀富有机质沉积岩建造、区域构造、区域建造、放射性异常信息和综合预测标志等,提出并阐述“小凹陷成大矿”条件;系统建立渗出砂岩型铀矿床预测定位标志体系,特别是野外可识别的宏观标志,包括控矿构造、沉积建造、蚀变改造、铀矿化砂岩颜色、外来有机质特征等,并对比了渗入和渗出砂岩型铀成矿预测标志。提出的渗出砂岩型铀矿识别标志体系不仅对区分“渗入”和“渗出”两种矿化成因,而且对厘清控矿要素、指导成矿预测和找矿工程部署具有重要意义和价值。

湘西北北部地区黑色岩系铀多金属成矿环境研究

湘西北北部地区主要包括晓坪坳陷、慈利断陷盆地等区域,是湘西北成矿带上有用元素种类和矿物类型最为丰富的地区。文章通过对湘西北北部地区开展系统的地质调查评价和取样分析,研究表明区内铀多金属矿化形成环境主要为深水环境向浅水环境的过渡区域,海洋中的边缘浅海环境具有更佳的铀成矿条件。微量元素特征参数表明,研究区从震旦纪到寒武纪海洋环境是由相对富氧向缺氧环境的转变,寒武纪在海水缺氧的大背景下,发生过一到两次短时间小规模的充氧事件。对U、Th、稀土等元素的研究表明湘西北北部地区从震旦纪晚期到寒武纪早期U的富集速率明显加快,而后U富集速率逐渐降低,指示研究区在寒武纪早期海洋中的热水作用最为强烈,而后逐步减弱,且成矿作用过程中有深部物质的参与,矿化越好,受深部热水影响越强。对Ce的研究结果表明,研究区震旦纪到寒武纪在大的海退背景下存在3个较为明显的海平面“升-降”转化界面,可以将这段地质历史划分为4个海平面升降变化阶段,在海平面升高阶段,沉积物中Ce异常减小,海洋中还原性增强,有利于有机质和铀多金属元素的富集。研究区矿物学方面的发现与通过地球化学方法得出的结论具有较好的一致性,晶质铀矿、铀石等矿物的晶型、共生关系和所包含的Y、Se等元素指示寒武纪时期研究区黑色岩系成矿处于较高温度、强还原的条件下,且海底热流喷涌过程中携带有深源物质参与成矿。

铀资源勘查技术国际科技前沿动态

铀资源勘查技术兼具核科技与地质勘查技术的双重属性,是支撑铀矿勘查不断取得突破的根本动力。全面了解、掌握国外铀资源勘查技术的前沿动态,不仅对发展具中国特色的先进铀资源勘查技术体系具有重要意义,而且对国内铀资源勘查生产亦具有重要借鉴意义。基于大量资料文献的调研、研判及综合分析,概略介绍了铀资源无人机探测、铀资源高精度多维探测、基于大数据的铀资源勘查与预测评价、高效低成本探测等4个技术方向当前国际上的主要研究内容、前沿或热点、重要进展或标志性成果,并结合新时期我国天然铀高质量发展的需求,提出了相关技术国际前沿动态对我国铀资源勘查技术发展的启示。

松辽盆地海力锦铀矿床黄铁矿微量元素、硫同位素特征及其对成矿流体性质的指示

海力锦铀矿床控矿灰色砂岩垂向上具有“两红夹一灰”特征,铀矿体呈多层板状,与传统的层间氧化带砂岩型铀矿明显不同。文章通过对赋矿灰色砂岩中黄铁矿微区微量元素和硫同位素特征研究,反演海力锦铀矿床成矿流体性质及来源,主要获得了以下几点认识:(1)海力锦铀矿床含矿层黄铁矿赋存形式包括胶状、草莓状,铀矿物常与草莓状或胶状黄铁矿共伴生于有机质胞腔内或矿物粒间孔隙。(2)黄铁矿微量元素特征显示,As、Mo、Sb等亲硫性元素从核部到边部含量增高,Mo、Ni、Zn、Cu、Ba等元素与U具有较好的正相关性,这些元素在大气降水中难以沉淀和富集,往往富集于深部还原性流体中。硫同位素δ34SV-CDT值显示从核部到边部明显降低的特征,表明黄铁矿形成环境发生了较大改变,指示海力锦铀矿床成矿流体可能为深部具有一定温度的还原性流体。(3)松辽盆地西南部深部发育厚度大且面积广的富铀烃源岩,海力锦铀矿床东南部F1断裂为沟通深部富铀烃源岩和含矿层的深大断裂,据此认为海力锦铀矿床成矿流体可能来自深部还原性流体(富铀烃源岩),控矿灰色砂岩为还原性流体对原生氧化沉积建造的还原改造。

松辽盆地西南部大林地区铀成矿特征分析

大林铀矿床是松辽盆地西南部新近探明的砂岩型铀矿床。文章对大林铀矿床的矿体产出特征、铀的赋存状态等成矿特征开展研究。研究表明,宏观上,含矿层姚家组下段氧化砂岩十分发育,铀矿体呈多层产出且受氧化带控制明显。微观上,铀主要呈吸附态,独立铀矿物与含铀矿物较少,沥青铀矿是主要的独立铀矿物,存在含钛铀矿物与闪锌矿的热液矿物组合。根据成矿特征初步判断,大林铀矿床与邻近的钱家店铀矿床和宝龙山铀矿床成因相似,是表生流体与深部流体叠加作用的结果。

砂岩型铀矿形成的新模式:来自深部有机流体的成矿作用

已有的铀成矿模式大多认为,砂岩型铀矿是浅表层含氧水从盆地周邻蚀源区析出携带的外源铀汇入盆地而成矿。本研究发现,鄂尔多斯盆地北部伊盟隆起东部砂岩型铀矿矿集区的地质演化、地貌特征和铀成矿与此成矿模式相悖。其中令人困惑的关键问题是铀成矿物质的来源。对研究区的代表性矿物铀石(形成于强还原环境)及其共生的矿物进行多种地球化学测试分析发现:铀矿区存在淡水低温和中高盐度热液两类截然不同的铀矿化环境;铀成矿年龄主体小于80 Ma。结合盆地煤系气源岩富铀、天然气耗散量巨大和在伊盟隆起发现大面积分布的多种与成熟煤型气耗散有关的蚀变产物和凝析油苗,综合相关模拟实验和测试分析,提出了铀源来自深部的铀成矿新模式:来自盆地中部深层富铀煤系地层中的溶气热流体,在向伊盟隆起东部高部位运移耗散过程中,萃取并携带母岩和沿途围岩富铀地层中的铀元素运移到浅层,随温压降低亮晶方解石与铀石相伴沉淀完成了热液成矿过程,被析出的大规模有机天然气则在浅表层低温成矿同时为铀矿的保存创造了还原环境。此铀成矿新模式拓展了盆地勘探铀矿的思路和领域,提升了多种能源矿产相互作用的成矿效应和综合评价预测的科学性。

地浸采铀注液井小直径潜水泵抽水洗井试验

某地浸采铀试验采区注液井周边含矿层堵塞严重。注液井套管内径仅有80 mm,在常规空压机抽水洗井结束后,在3口注液井中开展了小直径潜水泵抽水洗井试验。初始抽水量均在4.5 m_(3)/h左右,期间最小抽水量为3.4 m_(3)/h,其中2口井的第1股最浑浊洗井水的含砂量分别为4.36、5.19 kg/m_(3)。粒度、电镜扫描和化学组成分析显示,洗井水沉降干渣中的矿物碎屑主要为粉砂、细砂碎屑,少量黏土碎屑;化学沉淀主要是CaCO_(3)、MgCO_(3)和FeCO_(3);潜水泵抽水洗井累计运行约27.5 h,未出现任何故障。试验表明,小直径潜水泵抽水洗井可行且投资少、成本低、安全性高、实施方便。