海水中234Th的超低水平液闪谱仪测定

本文提出了利用超低水平液闪谱仪测定海水中234Th的方法.海水经氢氧化铁吸附共沉淀富集后,接着用阴离子交换和TBP/煤油萃取进行Th同位素的分离与纯化.对一系列测定条件进行了详细的研究,提出了测定海水中234Th的适宜程序,即在含有234Th和产额示踪剂230Th的纯化后的5mol/dm3HNO3溶液中加入TBP/煤油进行萃取,然后用0.1mol/dm3HNO3反萃取,后者是先用契伦柯夫计数法测量234Th(通过234mPa),后加入闪烁液Hisafe 3用α/β模式测量α放射体230Th.对于α和β放射体液闪谱仪的计数效率分别为100%和55.7%±2.7%.234Th的化学回收率和总探测效率分别为70%～80%和30%～45%.该法测定海水中的234Th快速、简便和高效.     

海水中228Th、234Th、228Ra的联合富集与测定

采用大体积现场泵方法同时采集不同粒级的^228Th、^234Th及溶解态的^228Th、^234Th、^228Ra．以小体积MnO2共沉淀-β计数法测定海水中的总^234Th活度（A＇TTh）；用Goflo采水器采集6～10dm^3海水，继而过滤收集颗粒物质并测定其^234Th的活度（A’PTh）；以α能谱测定分离纯化后的^228Th；对^228Ra则是采用测定其子体^228Ac的β放射性方法．采用此流程分析了南海2004年2月航次A1站住的样品，获得了较好的结果．     

基于NaI(Tl)伽马谱仪的反演分析法在海水放射性探测中的应用

伴随着核能的快速发展和应用,海洋放射性环境安全监测受到了越来越多的关注。因具有成本低、功耗低、探测效率高等优点,NaI(Tl)伽马谱仪成为海洋放射性自动连续监测主要应用的仪器。但是,该谱仪探测分辨能力尚存在不足,导致核素甄别和定量检测存在困难。为了解决该困难,本研究采用理论计算、仿真模拟和实验测量等技术手段,开展基于反演分析的海水伽马能谱处理分析方法研究。研究结果表明：仿真实验中经过反演分析法计算的重构谱线的分辨率得到大幅改善,与仿真能谱中核素的道址和活度的参考值相比,重构谱线的₁₃₄Cs、₁³⁷Cs、₆₀Co和₄₀K核素峰的道址误差在2道以内,活度计算误差在4%以内。在位于青岛的海洋科学实验站进行的海水现场实验结果表明反演分析法对₄₀K核素的活度分析结果为1.218×10₄ Bq·m_-³。该方法能够有效解决NaI(Tl)伽马谱仪探测分辨能力不足的问题,实现准确的海水放射性核素分析。     

海水U、Th长寿命核素的高精密度MC-ICP-MS测定方法

建立了适合海水U、Th同位素高精密度测量要求的MC-ICP-MS方法.确定了采用Mg(OH)2共沉淀法富集海水U、Th同位素时的最佳NH3·H2O浓度为0.14 mol/dm3.采用CRM-145 U标准溶液,经质量分馏、电子倍增器增益、丰度灵敏度、仪器及试剂本底和记忆效应等校正后,历时3个月得235U/238U和234U/238U的准确度分别优于0.05%和0.08%,精密度分别优于0.12%和0.10%.将该方法应用于台湾海峡B9站位3份平行水样中U、Th同位素含量及比值的测定,得238U平均含量为3.05±0.05μg/kg,234U/238U平均值为(6.28±0.11)×10-5,U含量及其同位素比值的标准偏差均小于3%;232Th的平均含量为(1.66±0.04)×103pg/kg,232Th/230Th平均值为(1.95±0.01)×105,Th含量及其同位素比值的标准偏差均小于2%.测定结果与海区的水文学条件及物质来源相吻合,证明了方法的可靠性.     

海洋沉积物中226Ra、210Pb和U、Th同位素联合分离测定的研究

本文建立了一个联合分离测定沉积物中226Ra、210Pb和U、Th同位素的方法,讨论了这些核素之间的分离、纯化以及影响化学回收率的因素,报道了此法的一些应用.     

海水中~(137)Cs的分析方法

本方法采用磷钼酸铵(AMP)预富集CS,在弱酸介质中以氯铂酸铯形式沉淀、制源,进行β放射性测量,求海水中~(137)Cs的含量。方法的灵敏度为4.3×10~(-4)Bq/L,全程化学回收率和放化回收率分别为74.6±13.3％和71.4±3.3％。对~(40)K和~(87)Rb这两个干扰核素的去除率分别为100％和96％。     

海水中铀的测定

江河湖水资源调查,水源污染控制以及海水提铀工作的开展,都促使人们开展对微量铀分析的研究.天然水中微量铀的分析大体上由二步组成,一是从大体积水样中浓集铀,二是浓集物中铀的分离和测定.人们广泛采用的富集方法之一是吸附共沉淀法(作为吸附剂有Al(OH)₃[1]、Fe(OH)₃[2]、活性炭[3]、AlPO₄[4]等)、胶体吸附浮选法以及有机共沉淀法等.     

海水中多氯联苯的气相色谱分析方法

本文叙述了用于测定天然海水中多氯联苯的气相色谱分析方法,本法采用国产1300(1)型树脂提取富集天然海水中PCB_s,在2000ml空白海水中添加100ng PCB₅/l,让其通过树脂柱,树脂柱对多氯联苯的平均富集效率为87.4%样品提取液通过微型硅胶混合层析柱,旨在净化与分离经与同类的分析方法比较,本方法使用有机溶剂及固体吸附剂用量少,既经济、省时,又可降低分析过程的试剂空白值。本方法用普通氮气代替K-D浓缩器浓缩样品提取液,操作简便快速。用2000ml空白海水与2000ml天然海水分别添加25-125ng PCB₅/l的标准溶液,让外加标准的海水样品通过分析全过程,其平均回收率在66-73%,变异系数在±10%之内,试验结果表明,本方法适于测定表层海水中ng/l级的多氯联苯。     

南沙海域基于234Th-238U不平衡的颗粒态有机碳输出通量研究

利用234Th-238U不平衡方法研究南沙群岛海域春季真光层颗粒动力学性质,测定了4个站位水柱中颗粒态有机碳(POC)、溶解态及颗粒态234Th和238U的含量,讨论了各站位水柱中234Th/238U)A.R.的垂直分布.运用稳态箱式模型计算各站位不同水层中溶解态234Th相对于清除至颗粒物的平均停留时间和颗粒态234Th相对于迁出作用的平均停留时间.结合POC/234ThP比值,用两种方法估算出各站位的颗粒态有机碳输出通量分别为8.51-34.94和13.28-50.06mmol·(m2·d)-1.两种方法结果一致,说明234Th是表征POC循环的良好示踪剂.     

X-射线荧光光谱法定量分析海山富钴结壳中MnO2与MnO的含量之比值

通过普通X-射线荧光光谱仪,结合PeakFit谱峰处理软件,对不同比例的MnO和MnO₂的混合样品的K_β谱峰参数进行了研究,用数学方法将实测的谱峰分解为各个单一的谱峰参数(峰位、峰高、半高宽、子峰面积),找出了各个谱峰参数与不同价态锰的含量之间的关系,并据此确定了中太平洋海山区大量富钴结壳样品中不同价态锰的相对含量.分析结果显示,富钴结壳中+4价锰从核心向外有增高的趋势,可以认为这与该区第三纪以来南极底流活动的增强有关.     

An intercomparison of small- and large-volume techniques for thorium-234 in seawater

In this paper, an intercomparison of methods for the determination of ²³⁴Th in seawater is discussed. Samples were collected either from a shore-based 600 m water source, or from standard bottle casts in deep waters off Hawaii and the Southern Ocean. We compared large-volume techniques, which rely upon Mn cartridges for the collection of dissolved ²³⁴Th and its detection via gamma counting (>200-l samples), with small volume methods that employed either direct beta counting, or beta counting after radiochemical purification (2–20-l samples). Unique to this study is the presentation of small volume (2 and 5 l) ²³⁴Th methods. This new technique is an adaptation of 20-l methods that are based on the coprecipitation of thorium with Mn oxides followed by direct beta counting of the precipitate. The small volume Mn coprecipitation methods were found to be superior to other methods due to ease of sample collection, processing and low overall analytical uncertainties.     

Measuring low concentrations of Th in water and sediment

²³⁴Th/²³⁸U disequilibria have been used extensively in studies of particle dynamics and the fate and transport of particle-reactive matter in marine environments. Similar work in low salinity, estuarine, and freshwater systems has not occurred primarily because the lower concentrations of both parent and daughter nuclides that are typical of these systems often render established methods for the analysis of ²³⁴Th inadequate. The application of this radionuclide tracer technique to these systems, however, has great potential. To this end, we present a method for measuring low activities of ²³⁴Th in relatively small samples (<200 l) using low background gas-flow proportional counters, a ²²⁹Th yield monitor, and empirical corrections for the interferences from real and apparent betas that are emitted by other thorium isotopes and their progeny. For samples with low ²³⁴Th/²²⁸Th activity ratios, we improve upon current beta counting methodologies that rely on immediate sample counting, weak beta absorption, or multiple beta counts so that, using the analytical approach outlined here, it should be possible to measure ²³⁴Th activities (i) as low as 1.5 dpm/total sample, (ii) up to 2 weeks after radiochemical purification of thorium, and (iii) with only one sample count for alpha and beta activity.     

三种体系萃取分离-液闪测定海水中234Th的比较研究

本文对TOA萃取剂萃取钍适宜的操作条件及萃取溶剂进行了试验,提出了TOA/苯萃取234Th的最佳条件: 在 1cm3含 234Th的 6mol/dm3 HNO3 溶液中,用体积比为 0. 5的TOA/苯溶液 2cm3 萃取,然后用 2cm3 1. 0mol/dm3 H2SO4反萃取,最高萃取率达 94%.对TOA/苯、TBP/煤油和TTA/苯这 3种萃取体系的萃取效率及其影响因素、萃取机理、成本等做了比较,认为 3种体系各有利弊,但均可有效地应用于相关的海洋学研究中.     

A single vs. double spike approach to improve the accuracy of Th measurements in small-volume seawater samples

²³⁴Th is a particle-reactive radionuclide widely used to trace biogeochemical oceanic processes occurring over short timescales. During the last few years, small-volume techniques based on the co-precipitation of ²³⁴Th with MnO₂ coupled with beta-counting have been developed as an alternative to large volume gamma-spectrometric techniques. Here a procedure has been developed to enhance quantitative measurement of ²³⁴Th in MnO₂ precipitates. The main objectives were to obtain a purified Th fraction for beta-counting and to determine the chemical recovery of ²³⁴Th using Th spikes and alpha-spectrometry as an alternative to ICP-MS based methods. Two variations of the procedure are presented. In the first “1 spike” method a ²³⁰Th tracer is added to the sample prior to precipitation of MnO₂, and UTEVA® extraction chromatography is used to obtain a NdF₃(Th) purified source that can be used for both beta-counting of ²³⁴Th and alpha-spectrometry of ²³⁰Th. In the “2 spike” method a ²³⁰Th spike is added and the MnO₂(Th) precipitate is directly beta-counted for ²³⁴Th and subsequently spiked with ²²⁸Th or ²²⁹Th prior to UTEVA® purification and alpha-spectrometry. The results confirm the need to process small-volume seawater samples for ²³⁴Th measurement in presence of a yield tracer, and show that both the 1 spike and 2 spike methods allow an accurate and precise determination of ²³⁴Th (relative percent difference, RPD, between expected and mean measured value < 1%; CV between replicate samples < 3%). Our work also suggests that, although the combined analytical uncertainty on total ²³⁴Th measurements accomplished with both versions of the NdF₃ procedure is promising (6% for 2-L samples), the precision of the ²³⁴Th flux estimation will ultimately depend on the degree of disequilibrium between ²³⁴Th and ²³⁸U.     

Application of vertically integrated sampling approach to study of new production via 234Th-238U disequilibria

I~IOWBecause of the imPOrtance of new production in the studies of the structure and function ofmarine eCOSystem and carhan cycleS, one should pay great attention tO the study of new production in biological oceanography, biogeOChendstry, and especially in the study of global change(Plait et al., 1992; Jiao and Wang, 1993; Wang, 1992). With the deepening of the study ofnew production, it has been found that the spatial and temporal distributions of new preductionvary largely in different…     

Determination of thorium isotopes in seawater by moored MnO2-fiber method

A method is described for the determination of Th isotopes (²³²Th,²³⁰Th,²²⁸Th and²²⁷Th) in seawater through analysis of Th adsorbed on MnO₂-impregnated fiber that has been moored in the deep sea for up to 10 months. Since the MnO₂-fiber adsorbs Th from seawater at a constant rate, natural²³⁴Th can be used as a yield monitor by making a correction for its decay during the period of deployment. The results obtained by the method showed good reproducibility and accuracy. The method has the advantage over the chemical coprecipitation method that the time and labor for sampling and processing a large-volume of seawater is reduced.     

南大洋普里兹湾基于234Th/238U不平衡法的POC输出通量研究

中国第22次南极科学考察(2005年11月至2006年3月)期间,测定了南极普里兹湾海域5个站位的从表层至150 m水深的不同层位水样中溶解态和颗粒态234Th,238U的放射性比活度以及颗粒有机碳.利用234Th/238U在上层水体中的不平衡,计算了南极普里兹湾上层水体中234Th的平均停留时间和输出通量.结果显示,随着纬度的增加,上层水体中颗粒态和溶解态234Th的平均停留时间总体趋向减小,并在中纬度站位出现了最低值,分别为1~8和29~48 d,而颗粒态和溶解态234Th的输出通量则在中纬度站位出现了最大值,分别为21~38和26~39 dpm/(m3·d).运用箱型清除模式,利用两种不同的方法估算了各水柱中从真光层底部输出的POC通量,平均值分别达到104.7 mmol/(m2·d)(E法)和120.6 mmol/(m2·d)(B法),表明南极普里兹湾夏季存在很高的新生产力,它将会对该海域碳的生物泵过程产生重要作用.     

Determination of cosmogenic 32P and 33P in environmental samples

Understanding phosphorus dynamics in marine environment is of great importance, and appropriate tracers for phosphorus cycling in oceans are invaluable. In this study, two methods were developed for extraction, purification, and determination of naturally occurring 32P and 33P in rainwater, marine plankton and sediments using both a low-level beta counter (LBC) and an ultra-low-level liquid scintillation spectrometer (LSS). Blanks, chemical yields and counting efficiencies were quantified for both methods. The chemical purification of 32P and 33P separated by both procedures was validated by their decay curves. The absorber thickness of aluminum for LBC was assessed as 39.2 mg/cm 2 . 32P and 33P specific activities in some rain samples were determined by both methods and showed good consistent results. The advantage of the LSS over the LBC is apparent in its high counting efficiency and in determining samples with high concentration of stable phosphorus. However, when measuring environmental samples with low concentration of stable phosphorus, such as rainwater, both methods can be used and each has its distinct advantage.     

A practical method for the simultaneous determination of234Th,226Ra,210Pb and210Po in seawater

A practical method has been developed for the simultaneous determination of²²⁶Ra,²³⁴Th,²¹⁰Pb and²¹⁰Po in seawater. In the method, the samples are spiked with²²⁸Ra,²³⁰Th,²⁰⁸Po and common lead to determine chemical yield. These nuclides are coprecipitated with calcium carbonate and ferric hydroxide from 20 to 50 l of seawater and separated from one another by using coprecipitation and ion exchange techniques. Counting sources of Ra and the other nuclides are prepared by electrodeposition onto silver discs. Their radioactivities are counted with an-spectrometer and a low background-counter. This method gives a standard deviation of about 5% for replicate determination of²²⁶Ra and the other nuclides.     

厦门湾水体中234Th的垂直分布及其时间变异特征

１９９６年 ９～１０月在厦门湾上屿附近海域定点站连续６个航次测定了水柱中溶解态（ＤＴｈ）、颗粒态~(２３４)Ｔｈ（ＰＴｈ）和溶解态~２３８Ｕ,获得了~２３４Ｔｈ的时空分布图象。研究海域水柱中ＤＴｈ、ＰＴｈ和总~２３４Ｔｈ（ＴＴｈ）的放射性比度分别在０．８０～３．９５山／ｍ~３、１,９３～５．６５Ｂｑ／ ｍ~３和 ３．４７～９． １８Ｂｑ／ｍ~３之间,整个水柱中 ＤＴｈ、ＰＴｈ和ＴＴｈ均与~(２３８)Ｕ呈不平衡,其特征是~(２３４)Ｔｈ亏损,且亏损程度明显大于大洋水体。颗粒态~(２３４)Ｔｈ和总悬浮颗粒物（ＴＳＭ）在水体中的分布及其随时间的变化趋势相当一致,非生物过程可能对近岸海域水体中~(２３４)Ｔｈ的分布起着非常重要的作用。