ICP-MS measurement of uranium and thorium contents in minerals in China

The activity levels of long-lived radionuclides in minerals have received more and more concern for the public health. The inductively coupled plasma mass spectrometry was used to measure the content of uranium and thorium in 60 mineral samples collected from 16 mines of seven provinces in China. The contents of uranium and thorium ranged0.17 ± 0.04 lg g^(-1)to 15.3 ± 2.39 lg g^(-1), and 0.19 ± 0.04 lg g^(-1)to 19.6 ± 7.56 lg g^(-1), respectively. The highest levels of U and Th contents were found in aluminum ore,whereas the lowest was found in antimony and copper ores.

Separation Behavior of U(VI) and Th(IV) on a Mixed Ion Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Determination of Trace Level Thorium in Uranium Matrix Employing High Performance Ion Chromatography

Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.

Factors Controlling Low Uranium and Thorium Concentrations in the Cayirhan Bituminous Shales(CBS)in the Beypazari(Ankara)Area,Turkey

In this study uranium and thorium contents and depositional characteristics of ay rhan bituminous shales（ BS）, west of Ankara（central Anatolia）, are investigated. Samples used were collected from boreholes opened by Park Holding Ltd. A total of 25 samples were taken from bituminous shale levels in boreholes drilled at 6 different locations in the study area. The H rka formation which hosts bituminous shale deposits is a volcanosedimentary sequence and all lithofacies indicate that a lacustrine environment where the water level was continuously changed. In addition to hydrocarbon generation potential, bituminous shales also accumulate significant amount of radioactive elements such as uranium and thorium. The average uranium and thorium concentrations of BS（1.83/2.62 ppm） are much lower than averages of UC, NASK and PAAS（uranium： 2.70/2.66/3.10 ppm; thorium： 8.50/12.30/14.60 ppm）. Low uranium contents in comparison to those of similar lacustrine environments might be attributed to that waters of depositional environment of BS contain low concentration of dissolved uranium and redox conditions were of oxic and dioxic character. Correlation data indicate that U and Th have a similar source and are associated predominantly with clays and phosphates and dominantly with organic material. Radioactive elements in the basin might be derived from Paleozoic granites and metamorphites（e.g. gneiss, schist） which comprise the basement and volcanism which was active in the region throughout the Miocene period. These elements are probably associated with uraniferous phosphate minerals（e.g. autunite, torbernite） which occur in granite, gneiss and schist. BS with average TOC content of 10.96 % shows very good/perfect source rock potential. Positive correlations between Gamma-Ray values and U, Th and K concentrations imply that radioactivity might be originated from these three elements.

An in-situ analysis and measurement of thorium-234,uranium isotopes in seawater

A low-level β counting-or spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium- 228 simultaneously and an easy operating procedure for the enrichment, radiochemical separating, sampling and measurement of thorium-234 and uranium-238 in the ocean are developed based on the requirements of analyzing export productivity in the eupho- ric zone via thorium-234 - uranium-238 radioactivity disequilibrium. The detecting efficiency both of 13 and α radiation is higher than 20%. The background of βradiation is less than 0. 5 min ^-1 , and the energy resolution of ct detector is better than 1%. Total recycle ratio of thorium-234 is about 75%. Using the above apparatus and procedure, the radioactivities of dissolved thorium-234 and uranium-238, particle thorium-234 and uranium-238 in seawater of the South China Sea, the Southern Ocean and the Arctic Ocean were analyzed.

The investigation on particulate organic carbon fluxes with disequilibria between thorium-234 and uranium-238 in the Prydz Bay,the Southern Ocean

Dissolved and particulate thorium-234, particulate organic carbon in the upper 150 m of water columns from five stations in the Prydz Bay, the Southern Ocean were determined during the 22nd Chinese National Antarctic Research Expedition （from November 2005 to March 2006 ）. The disequilibria between thorium-234 and its parent uranium-238 in upper layer was used to derive the averaged residence time of thorium-234, which decreased along with the latitude to the south and a minimum value, 1 - 8 d for particulate thorium-234 and 29 - 48 d for dissolved thorium-234, appeared at the medium latitude station, and the export fluxes of thorium-234 were calculated too and ＇a maximum value, 0. 35 -0. 63 Bq/（m^3 · d） for the particulate thorium-234 and 0. 44 -0. 65 Bq/ （m^3 ·d） for the dissolved thorium-234, appeared at the same station. The export fluxes of particulate organic carbon at different water columns were derived by two methods with irreversible scavenging model, and the averaged values were 104. 7 mmol/ （ m2 · d ） （ E method） and 120. 6 mmol/（ m2·d ） （ B method ）, respectively, indicating that a relatively high new production would exist in summer in the Prydz Bay where it will play a potential significant role in sequestering the absorption CO2 to deeper ocean.

Influence of Co-Solvent on the Extraction Behaviour of Uranium and Thorium Nitrates with Organophosphorous Compounds

Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical carbon dioxide (Sc-CO2) modified with various organophosphorous compounds such as dialkylalkyl phosphonates, trialkyl phosphates and trialkyl phosphine oxides in the presence of co-solvents such as methanol, dichlormethane and n-hexane. The influence of ligand and co-solvent on the extraction of the metal nitrates was studied in detail. These studies have established that co-solvent plays an important role in the extraction as well as fractionation of uranium and thorium nitrates. Polar co-solvent, methanol provided faster extraction without fractionation whereas the non-polar solvent, e.g. n-hexane provided some fractionation of metal nitrates though the extraction kinetics was slower.

Simultaneous Determination of Uranium and Thorium with Standard Dual-addition Method

dual-standard addition method was proposed and the principle of simultaneous determination for a interfering binary mixtures was discussed. The proposed procedure was applied to spectroscopic analyses for the simultaneous determination of uranium and thorium without prior separation. Various molar ratios of uranium/thorium, from 0.5∶1 to 10∶1, can be determined with satisfactory precision and accuracy. Uranium and thorium content in a phosphate ore and simulated sample were determined, the recoveries were 98.4%～102.5% for uranium and 96.8%～102.3% for thorium, the relative standard deviations (R.S.D) were 1.5%～2.3% for uranium and 2.1%～3.1% for thorium.

Solvent extraction of nitric acid, uranium(VI) and thorium(IV) by N,N,N',N'-tetrahexylsuccinylamide

A new kind of diamide N,N,N’,N’-tetrahexylsuccinylamide（THSA） was synthesized, characterized and used for the extraction of HNO3, U（VI） and TI（IV） in a diluent composed of 0.5 volume fraction 1,2,4-trimethy benzene（TMB） and 0.5 volume fraction kerosene（OK）. Extraction distribution coefficients of U（VI） and TI（IV） as functions of aque- ous nitric acid concentration, extractant concentration, temperature and salting-out agent （LiNO3 ） have been studied, and it is found that THSA as an extractant is superior to TBP for extraction of U（VI） and TI（IV）. Back extraction was also studied. At low acidity, the main adduct of THSA and HNO3 is HNO3.THSA. THSA.（HNO3）2 and THSA.（HNO3）3 are also found at high acidity. The compositions of extracted species, apparent equilibrium constants and enthalpies of extraction reactions have also been calculated.

Characterization of Crude Oil, Asphaltenes Based on Bismuth (Bi), Thorium (Th) and Uranium (U) Levels: Potential Environmental Impact

The actinides (Th, U) and bismuth exist at ultra-trace levels in petroleum and have rarely been reported to characterize combustible fuels. However, high-performance mass spectrometry coupled with plasma technology has succeeded in reaching detectable limits in the ng/L range, and has thus made such characterization possible. Crude oil is used as sludge for certain agricultural purposes;and asphaltenes are converted to by-products for constructing car parks, pavements, roofing material and thoroughfares. Our study uncovers an area that has not been previously explored and we examine the potential ecotoxicology of bismuth, thorium and uranium in this context. Asphaltene derivatives were separated from crude oil samples via multiple-stage soxhlet extraction. The virgin crude oil and isolated asphaltenes were investigated for Bi, Th and U content using a high-powered hyphenated facility. A Perkin Elmer SCIEX DRC-e ICP coupled to a quadrupole mass spectrometer was employed to detect the elements of interest. The levels of these elements occurred in the mg/L (ppm) and μg/L (ppb) ranges and were compared for crude oil and asphaltenes. The data showed higher levels of the detected elements in the asphaltene phase. The feasibility of applying the experimental results as a fingerprinting tool for provenancing crude oil and asphaltenes was examined. The results are discussed from the perspective of bismuth and actinide pollution and its long-term impact on sustainable development.

独居石优溶渣浸出过程研究

独居石是典型伴生铀、钍的稀土矿资源,通过现有的碱溶转化、优溶等步骤提取稀土后,所得优溶渣是富含铀、钍、稀土的重要二次资源。为与稀土提取保持一致的盐酸体系,研究优溶渣的盐酸浸出过程对整体回收工艺十分关键。采取单因素试验考察浸出过程条件对铀、钍、稀土浸出率的影响。结果表明,使用下述优化参数:盐酸浓度6 mol/L、浸出时间1.5~2 h、浸出温度60℃、液固体积质量比3 mL/g时,优溶渣中铀、钍、稀土的浸出率分别可达90%~95%、92%~93%、>60%,实现了较高的资源回收率。浸出渣的工艺矿物学分析表明,其主要由锆石、钍化合物和石英等脉石矿物组成。剩余的稀土组分则主要集中在未分解的独居石中,其余为少量磷钇矿和褐钇铌矿。试验结果可为独居石优溶渣的综合回收技术提供基础数据和支撑。

氯离子体系铀溶液中铁、钍、稀土的去除研究

采用复盐沉淀法,用硫酸钠同时去除氯离子体系铀溶液中的铁、钍、稀土杂质离子,并研究了硫酸钠用量、反应温度、反应时间、体系pH等对除杂效果的影响。结果表明,反应的最佳条件为:硫酸钠用量为理论量的160%、反应温度95℃、反应时间2 h、体系pH=0.75~1.25。在此优化条件下,铁、钍和总稀土的平均去除率分别达到99.62%、99.42%和98.27%,铀的平均回收率为99.87%。方法具有除杂效果好、铀损失率低、易分离等优点。

某独居石优溶渣二段逆流浸出试验研究

针对某独居石优溶渣,研究了采用一段常规浸出—二段逆流浸出工艺浸出铀、钍、稀土。考察了各因素对浸出效果的影响。结果表明:采用一段常规浸出法时,适宜条件下的铀、钍、稀土浸出率分别为98.66%、95.37%、64.23%;采用二段逆流浸出法时,铀、钍、稀土浸出率均可提高0.5%~1.0%,浸出液余酸降低50%以上,矿浆固液分离性能得到了一定改善。

混凝-共沉淀法处理含铀钍废水的研究

在核燃料元件研制和生产过程中,由于各种先进燃料元件掺杂元素种类不同,废液中除放射性污染物铀化合物外,还含有由燃料掺杂产生的钍(Th)等金属元素化合物。在含铀钍废液共沉淀过程中,钍盐还可以作为混凝剂对铀进行去除和净化。实验结果表明:对于含铀钍废液混凝-共沉淀体系,壳聚糖作为絮凝剂絮凝效果较好,废液中初始铀浓度越高,铀去除率越高,但铀浓度增加至60 mg·L^(-1)时,铀浓度的升高对铀去除率的影响就不再显著;钍铀比在低浓度铀([U]=20~60 mg·L^(-1))废液中对铀去除率影响较为显著,当钍铀比为1∶1时,铀去除率趋于平衡,在较高浓度铀([U]=60~100 mg·L^(-1))废液中没有显著影响。壳聚糖的加入量控制在0.5~1 mg·mgU^(-1)左右;pH值控制在8左右处理效果较好。温度对铀去除率影响较小,温度升高铀去除率略有下降,总体而言铀去除率>92%,钍去除率>96%。

放射性铌铁精矿中铀钍的脱除及分离

通过对国内某企业进口放射性铌铁精矿进行工艺矿物学分析,确定该精矿的主要矿相为烧绿石,同时伴生钛铁矿和白云母,矿石中放射性元素U和Th的含量分别为0.27%和1.03%。针对该铌铁精矿,探索H_(2) SO_(4)-Fe(Ⅲ)、H_(2)SO_(4)-HF-H_(2)O_(2)、H_(2)SO_(4)-HF、H_(2)SO_(4)-HF-H_(2)O_(2)-(NH_(4))_(2)CO_(3)体系中U和Th的浸出及分离效果,最终确定H_(2) SO_(4)-HF-H_(2)O_(2)-(NH_(4))_(2)CO_(3)多段浸出工艺能有效实现U和Th的脱除与分离。U、Th的脱除率分别为100%和80%。基于研究提出了铌铁精矿U、Th脱除及分离工艺流程。

煤系铝土矿中铀与钍富集特征及其自然伽马异常响应

山西省煤系铝土矿资源丰富,深部铝土矿资源评价正逐步开展,为进一步确定煤中铝资源禀赋,探求高效勘查方法,以山西孝义地区上石炭统煤系铝土矿层为研究对象,选取并采集了3个钻孔的37个样品,应用显微光学分析、XRD、SEM、XRF和ICP-MS等技术方法,在分析煤系铝土矿层沉积环境和成矿物源的基础上,研究铝土矿中铀(U)、钍(Th)元素的赋存状态与富集成因,探讨U、Th元素的地球化学特征与自然伽马异常的响应关系。结果表明,研究区铝土矿层形成于海相碱性弱氧化为主的沉积环境,沉积过程中存在氧化、弱氧化–弱还原和还原环境,且氧化还原条件不断发生微弱变化;铝土矿与其顶板黏土岩(矿)物源相似,主要源自酸性岩浆岩,而底板铁质岩的物源则与玄武岩或钙质泥岩有关;铝土矿层U、Th元素异常富集主要受控于物源母岩类型及铝土矿、黏土矿物和含钛矿物的吸附能力;铝土矿中富集的U、Th元素是自然伽马高异常的主要原因,且Th元素的贡献较U元素明显。研究结果对划分煤系铝土矿和围岩、确定煤系铝土矿的层位及推测矿体厚度具有实际意义,并对开展深部煤系铝土矿勘探与开发也具有理论指导意义。

含铀钍氯化稀土溶液中离子交换法提铀

提出了一种利用铀酰离子与Cl^(-)的络合,从高稀土低铀的含氯体系浸出液中分离提取铀而将大部分的稀土元素和钍留在浸出液中的离子交换法。研究了离子吸附过程中体系pH和氯离子浓度等对吸附效果的影响。结果表明,在反应pH=0~1、Cl^(-)浓度7 mol/L的优化条件下,饱和树脂对铀的吸附量能够达到43.34 mg/g。后续采用7 mol/L HCl溶液酸洗和去离子水淋洗,回收钍和稀土的同时实现了铀的分离提取。该技术不改变传统稀土提取工艺流程,仅增加铀提取工艺技术单元,可实现铀的分离与浓缩,具有工艺流程短、不影响原有稀土提取工艺和矿产最大化利用的特点。

光释光测年中铀钍钾含量ICP-MS和XRF测量方法

光释光(OSL)测年包括等效剂量和环境剂量率的测量,准确测定铀钍钾含量是保证环境剂量率计算准确的重要环节,常用测量方法为电感耦合等离子体质谱与发射光谱法(ICP-MS/OES)联用,但铀钍钾不能同时测定,测量时间长。本文采用ICP-MS和X射线荧光光谱法(XRF)测定光释光沉积物样品中铀钍钾含量并用于环境剂量率的计算。在ICP-MS分析中,对高含量的钾采用电子稀释,减少进入检测器的钾离子,使铀钍钾离子在同一个数量级上,实现了高含量钾和低含量铀钍同时分析,方法检出限铀为6.38ng/L,钍为8.52ng/L,钾为926ng/L。研究了封闭酸溶法和敞口酸溶法对铀钍钾测定的影响,两种溶样方法处理10个沉积物和土壤标准物质,铀钍钾测定结果准确可靠,相对误差无显著差异,均在0~9.33%;但敞口酸溶法操作更简便,样品处理时间(约9h)短于封闭酸溶法(约60h),故ICP-MS分析时选取敞口酸溶法溶解样品。采用压片XRF法测定标准物质中铀钍钾的相对误差分别为4.78%~16.2%、1.20%~13.3%和0.00%~5.67%。ICP-MS和XRF测定20个渤海湾沉积物样品,计算获得环境剂量率的相对偏差在6%以内。XRF更适合测量钾含量高的释光样品;而ICP-MS测定铀钍的检出限更低,精密度和准确度更高,对于超痕量样品,该法测量结果更为准确。

电感耦合等离子体发射光谱法测定LiF-UF_(4)和LiF-ThF_(4)熔盐中主量金属元素的含量

氟锂铀(LiF-UF_(4))和氟锂钍(LiF-ThF_(4))可用作钍基熔盐反应堆的添加盐,在熔盐生产过程中需检测主量金属元素锂、铀和钍的含量。本工作采用硝酸和过氧化氢对氟锂铀样品进行前处理,采用硝酸铝溶解氟锂钍试样,以电感耦合等离子体发射光谱法为测量手段,为降低信号漂移的影响,以锰作为内标元素,建立了两种快速分析手段。当称样量为0.2 g时,该方法的精度均小于2%。氟锂铀加标回收实验中,Li回收率在99.6%~102.4%,U回收率在99.6%~101.8%。氟锂钍加标实验中,Li回收率在99.6%~102.3%,Th回收率在99.6%~102.4%。这些分析方法操作流程简单,耗时较短,测定结果准确,精密度高,适合大批量样品的快速分析。

利用地面γ总量转换为空气吸收剂量率进行环境辐射水平评价——以桂阳县潘家村和永兴县土桥村实测数据为例

在长期的铀矿普查中,我国积累了海量的γ总量数据资料,但应用这些数据进行放射性环境评价的研究极少。本文从γ总量和空气吸收剂量率的测量原理出发,通过梳理γ总量、放射性核素含量与空气吸收剂量率之间的关系,建立起地面γ总量与空气吸收剂量率之间的联系,分析了仪器参数对测量误差的影响,认为γ总量仪器bK/bU=2.287、bTh/bU=0.430时,测量的γ总量与空气吸收剂量率满足严格线性关系,因此γ总量仪器的bK/bU、bTh/bU值越接近这两个数值,测得的γ总量转换为空气吸收剂量率越准确;利用湖南省电离辐射计量站模型进行了γ总量转换为空气吸收剂量率的系数求解,并分析了误差,推测了仪器参数中钾的铀当量值、钍的铀当量值的大致范围;在郴州市桂阳县潘家村岩体和郴州市永兴县土桥村灰岩地区进行了γ总量、γ能谱、空气吸收剂量率的同点位实测,结果显示,当核素含量比CK/CU均值小于1、CTh/CU均值小于3时,利用γ总量(FD3013仪器测得)估算的空气吸收剂量率与利用Beck公式根据能谱估算的空气吸收剂量率的误差基本处于同等水平,均方根误差均小于15%。根据国内核素的CK/CU、CTh/CU均值,认为国内大部分地区可以利用由FD3013仪器(或类似性能仪器)测得的γ总量数据估算空气吸收剂量率。利用已有铀矿普查资料中的γ总量数据转换计算有效空气吸收剂量率,为快速大面积评估环境天然放射性外照射水平提供了方法参考。