LASER-INDUCED FLUOROMETRY FOR THE RAPID DETERMINATION OF TRACE LEVELS OF URANIUM IN SEAWATER

A laser-induced fluorometric method for the rapid determination of trace level? of uranium in seawater with the Modified Anti-interference Fluorometric Reagent for uranium (MAFG) is described. Only a sample volume of 1.5-2.5 ml is used in each determination and no pre-scparation and concentration steps are required. The analysis rate is a sample per 5 min. The relative standard deviation of ten replicate determinations on 3.44 ppb U of the natural seawater is 4.7%.     

海水中铀与碱式碳酸锌的反应级数及活化能

目前国外对碱式碳酸锌吸附海水中铀的报导较少,对其吸附海水中铀的反应级数及活化能测定的报导尚未见到。本文试图用三颈瓶反应器及分光光度法,测定海水中铀与碱式碳酸锌的反应级数及活化能,并获得较满意的实验结果。     

EXTRACTION OF URANIUM FROM SEAWATER BY AMIDOXIME RESINS

The adsorption behaviour for uranium of four kinds of amidoxime resinst RNH, RCH, RAH and RPH in seawater has been investigated. It has been found that all these resins are capable of adsorbing rapidly uranium from U-cnriched seawater with a high uranium uptake.RNH was able to adsorb uranium satisfactorily from natural seawater, and the uranium uptake of RNH with a degree of cross-linking of 3-5 mol % was above 200 μg/g-R (adsorption for 15 days). The uranium uptakes of RCH, RAH and RPH from natural seawater were much lower than the uranium uptake of RNH. The factors which caused the difference between resins RCH, RAH, RPH and resin RNH are discussed.     

莱州湾海水中U的不均匀分布规律及地球化学研究

本文报道了1984年和1987年莱州湾海水中U分布规律的调查研究结果。发现莱州湾海水中U存在着不均匀分布规律,其不均匀分布主要受黄河水高浓度U入海扩散、稀释的影响和控制;雨季,也受到附近河流输入的一定影响。调查结果说明,莱州湾海水中U浓度普遍较高,但尚未构成对海洋生物污染的影响。初步论证了莱州湾海水中U对形成沿岸地下浓缩海水高U浓度的影响。     

MECHANISM OF URANIUM ADSORPTION ON AMIDOXIME RESIN

The mechanism of uranium adsorption from seawater by polyacrylamidoxime resin is investigated by means of the experiments of adsorption isotherm and adsorption rate. The uranium uptake increases with the adsorption temperature and varies with the pH of seawater. Thermochemical and kinetic calculation show that the enthalpy change (△H) and the activation energy (E) of the uranium adsorption are 42.4 42.4 kJ mol-1 and 41.2 kJ mol-1 respectively, indicating that the uranium adsorption on the resin proceeds via a certain complex chemical reaction in which the amidoxime group in the resin chelates uranyl ions.     

ADSORPTION ACTION OF BASIC ZINC CARBONATE ADSORBENT ON URANIUM IN NATURAL SEAWATER

1. The adsorption action of basic zinc carbonate adsorbent on uranium in natural seawater can be expressed with the following formula of adsorption isotherm:C=k(U*)n = 8.51× 10-1(U*)0.49,where C is the concentration of uranium on adsorbent; U* is content of uranium in natural seawater employed.2. when the quantity of basic zinc carbonate adsorbent (T) is constant, with the increase of natural seawater quantity through the adsorption column (G), also increased are the adsorption content of uranium of the adsorbent (U), the concentration of uranium on the adsorbent (C) and the concentration of residual uranium (C0*) in natural seawater after adsorbing uranium, while the rate of recovery of uranium (R) is decreased. With the increase of (G) the coefficient of distribution (Kd) decreases to a certain value and then a little rises again.     

海水中微量元素无机离子交换动力学研究 Ⅳ.海水中铀(Ⅵ)与水合氧化钛离子交换反应的级数和活化能的测定

关于海水中铀(Ⅵ)与水合氧化钛的作用、国内外已有许多报导,内容包括水合氧化钛制备方法的不同对交换铀量的影响,水合氧化钛和海水中铀的基本物理—化学性质的研究及它们在反应过程中物理—化学性质变化规律的研究,海水中铀与水合氧化钛作用机理的研究等等。但对这一反应的动力学研究文献上报导极少,除了在本研究Ⅰ、Ⅱ和Ⅲ中报导的反应机理的研究[1,2]证明反应过程的速率由液膜扩散所控制之外,关于这一离子交换过程的反应级数和活化能的研究却至今未见有文献报导。     

Dissolved uranyl complexed species in artificial seawater

The distribution of dissolved uranyl species was calculated on the basis of the stability constants published elsewhere and compared with the results obtained from the experiments performed in artificial seawater. According to the distributions calculated and electrochemical and spectrophoto-metrical measurements performed in model electrolytes and artificial seawater (pH=8.2) in the presence of sufficient hydrogen peroxide, uranium most probably predominates in the form of a mixed uranyl-dicarbonato-hydrogenperoxo complex. The results obtained could be applied to the natural marine photic zone.The mixed complex has to be taken into account as an additional form of dissolved uranium species influencing their cycle in natural water systems. Recent discovery of the presence of hydrogen peroxide in the surface waters of seas has challenged a long-held notion of the prevalence of uranyl-carbonato complexes in seawater.     

钛胶海水提铀动力学研究Ⅲ——交换过程的扩散机理

水合氧化钛是一种无机离子交换剂.它对海水中铀的吸附是一种较为复杂的离子交换过程.除了一般的离子交换外,可能还伴随有络合[螯合][1]过程.在一般的情况下,离子交换的决定步骤是离子扩散.根据体系的性质不同,可以是离子在交换剂粒子内部的扩散(粒子扩散),或是在围绕粒子周围的液膜内部的扩散(液膜扩散).     

Adsorption of uranyl complex ions on hydrous titanium oxide (HTO)——Ⅱ. Infrared spectrum investigation

-The i. r. spectra of Na4 [UO2 (CO3)3], Na [UO2 (OH)3] and the surface species of uranium on HTO underthe condition of flowing natural seawater and concentrated seawater (NaCl-NaHCO3-U) were recorded, with the bands of urany! of surface species obtained and the finding that iigands of surface species besides HTO are mainly water and OH, and there are some CO32- groups under the condition of natural seawater. Some relations between the complex properties and the j. r. spectroscopic characters for uranyl complexes were studied, and the transferred change quantity of surface complex was calculated.Structure models for surface species of adsorption are herein presented and the mechanism for uranium adsorption is deduced.     

错流超滤技术在海水胶体态铀、钍、镭同位素和有机碳研究中的应用

建立了由预过滤装置、蠕动泵、中空纤维超滤膜(AmiconH10P10-20,标称截留分子量10KDa)和连接管组成的错流超滤系统,利用荧光标记的40KDa葡聚糖和已知放射性活度的234Th示踪剂评估了超滤膜的截留和吸附性质,探讨了234Th在超滤过程中的渗透行为,考查了该系统用于实际海水样品时铀、钍、镭同位素和有机碳的质量平衡状况.结果表明,10Kda中空纤维超滤膜对40Kda葡聚糖具有良好的截留效率(85%),而吸附损失率为18%.铀、钍、镭同位素和有机碳在超滤过程中均达到极佳的质量平衡,回收率R=95%～98%,优于大多数文献报道的值.234Th在超滤过程中的渗透行为可以很好地用渗透模型加以描述.研究组分胶体态含量占“溶解”态含量的份额大小顺序如下:钍同位素、有机碳、镭同位素约等于铀同位素,这与钍为强颗粒活性元素、铀和镭为水溶性元素的地球化学性质相吻合.     

Heavy metals in the benthic animals from hydrothermal vents: Results of neutron activation analysis

A series of samples of inhabitants of hydrothermal vents were collected during the 12th cruise of R/V Akademik Mstislav Keldysh in Guaymas Basin (the Gulf of California) and the Axial Seamount area (Juan de Fuca Ridge). The concentrations of trace and heavy metals in the tissues of Ridgeia piscesae, Riftia pachyptila, and Paralvinella palmiformis were analyzed. The neutron-activation analysis revealed significantly higher concentrations of uranium in the tissues of Paralvinella palmiformis as compared to the ambient seawater. The possible reasons for such phenomenon are discussed. The data obtained by the neutron-activation method are compared with those obtained by the atomic-absorption method for the same tissues analyzed.     

Study on the adsorptive complex wave of tin in seawater

A trace of tin exists in seawater, and is also probably in combination with organic materials or microbes. Therefore, it was reported that methods for determining tin in seawater need to use a separation or preconcentration stage in analysis. This paper provides an oscillopolarographic method for determining directly tin in seawater by irradiating it with ultraviolet rays. In a seawater system with 0.0035％ cupferron (Hcup), 0.0038％ Tween-80, 0.318 mol/1:0.375mol/1 NH_3 H_2O:HAc as a basic solution, there occurs a sensitive derivative     

Biogeochemical processes in a freshwater–seawater mixing zone in permeable sediments along the coast of Southern Brazil

The southern portion of the Brazilian coast is dominated by coastal lagoons formed by sandy barrier spits with small inlets. This coastal configuration is a barrier to the surface flow of freshwater to the sea; thus, we suspect that a significant amount of freshwater flows through the permeable sands, beneath the barrier spits, where it mixes with seawater. We excavated an 18-m-deep well into the barrier spit which separates the Patos Lagoon from the South Atlantic. Using this well, we were able to sample interstitial waters from discrete layers, at 1-m intervals, which were analyzed for salinity, temperature, pH, nutrients (ammonium, nitrate, phosphate, and silicate), uranium, molybdenum, and barium. Similar analyses were made on surface water samples from the Patos Lagoon estuarine mixing zone.Results of well samples show a continuous increase in salinity with depth reaching 18 at the bottom. Ammonium and silicate are high, generally around 100 and 100–150 μM, respectively, throughout the subterranean profile. Phosphate shows a distinct maximum at about 6 m (ca. 25 μM), and nitrate is generally low in all well samples. Uranium and molybdenum exhibit a minimum in the well profile at about the same location where barium exhibits a maximum (greater than 2 μM). When results are compared to the surface lagoon–seawater mixing data, ammonium, phosphate, silicate, and barium in well samples of similar salinity show considerable enrichment, while a comparison of uranium and molybdenum data indicates significant depletion of these metals in most well samples.Based on these and other data, we deduce that the following processes are active: products of remineralization of organic detritus accumulated in lagoon sediments are advected through permeable sediments to the oceans; dissolution of biogenic solids and/or solid silicates mobilizes silicate; phosphate, uranium, and molybdenum are mobilized from phosphate-rich sediment layers; sulfate reducers remove uranium and perhaps molybdenum from solution throughout most of the well profile; barium is desorbed from solids in the subterranean mixing zone. These results demonstrate that freshwater discharged to the ocean through permeable sediments may have a significantly different composition than that discharged at the surface.     

ON CHELATING RESINS FOR EXTRACTING URANIUM FROM SEAWATER

A number of dictating resins have been synthesized for extracting uranium from scawatcr. The feasibilities of extracting uranium directly from seawater by synthesizing chelating resins have been investigated by studying three factors:(1) the chelating ability of the resins for uranyl ion;(2) the competitive complex of calcium, magnesium and other cations with uranyl ion;(3) the competitive complex of carbonate ion with uranyl ion.It is suggested that the competitive complex of carbonate ion with uranyl ion should be the most important factor.     

厦门邻近海域海洋环境放射性水平及评价

良好的环境质量是厦门成为一个宜居和滨海旅游城市的重要基石。自日本福岛核事故发生和福建省核电站陆续运行之后,厦门邻近海域潜在的核污染风险受到公众和管理部门的关注。本研究测定了2015年2月和8月厦门邻近海域海水和海洋沉积物中主要放射性核素的含量水平,并据此评价了该海域的环境放射性质量状况。结果表明海水中总铀、90Sr、226Ra、137Cs处于我国海洋放射性水平变化范围以内,无明显季节差异,其他放射性核素58Co、60Co、134Cs、110mAg、59Fe、54Mn、65Zn均未检出,海水中90Sr和137Cs的活度最大值远低于国家海水水质标准限值,海洋沉积物中放射性核素活度水平亦在我国海洋放射性水平变化范围以内。利用我国现有的海洋放射性环境质量评价方法对厦门邻近海域放射性质量状况进行分级评价得出其海水放射性质量为2级,海洋沉积物放射性环境质量为1级,均属于安全级别。研究结果表明2015年在厦门附近海域未观测到放射性污染现象。     

海水为溶剂合成纳米粉煤灰沸石及其性能表征

以海水为溶剂,采用熔融法合成了纳米粉煤灰沸石。粉煤灰与NaOH的质量比为1:1.2,熔融温度550℃,熟料质量与海水固液的体积比为1:5(g/mL),晶化温度100℃,晶化时间6h。通过仪器分析和化学方法,对产物的结构、形貌、性能进行表征。同时,研究了产物的矿物组成、形貌、比表面积、阳离子交换量及化学组成。结果表明:产物为NaX型沸石和羟基方钠石的复合型沸石,海水晶化粉煤灰通过碱熔融法得到沸石质量优于传统水热法。合成沸石的性能和各项应用指标表明,所合成的沸石具有良好的实际应用价值。     

Fibrous adsorbent containing amidoxime and carboxyl groups and adsorption of uranium

Through introducing amidoxime and carboxyl groups into polyacrylonitrile fiber, a fibrous adsorbent with high capacity and fast adsorption rate was obtained, which could adsorb 4.6 mg uranium/g in 10 days from natural seawater. The influence of the functional group content on equilibrium adsorption capacity Xm and adsorption rate constant K of the adsorbent was studied, thus indicating that the contents of amidoxime and carboxyl groups correlated with Xm and K respectively. It is concluded that the amidoxime group is of reactive adsorption, while the carboxyl group is of promotion in the adsorption of uranium. In this paper, the mechanism of uranium adsorption on the fibrous adsorbent is deduced and the chelating structure of adsorption species is discussed with molecule orbit theory.     

海水淡化取水口空间选划适宜性评价方法与应用

海水淡化取水口空间选划受自然地理、生态环境和社会经济等多种要素的影响,对取水口工程建设的经济性、稳定性和安全性具有重要意义。在海水淡化取水口空间选划影响要素分析的基础上,针对浅海取水方式,从基础地理条件、水体环境条件、灾害条件和产业发展条件四方面筛选代表性评价指标,构建海水淡化取水口空间选划适宜性评价模型。以山东省荣成市近岸海域为研究区,基于GIS平台的多因素空间叠置分析实现初步的适宜性空间分区,然后叠加约束条件生成最终的海水淡水取水口选划适宜性空间分区结果,形成具有科学化、定量化和空间化特征的海水淡化取水口选划适宜性评价体系。本研究在理论方法和技术层面上完善了现有的海水淡化取水口空间位置选划方法,评价结果可为海水淡化取水口空间选划提供科学依据。     

海水中钾的测定——交流示波极谱滴定在海水分析中的应用(Ⅰ)

研究用交流示波极谱测定海水中钾的方法。海水试样用NaOH调节pH约12,加入过量四苯硼化钠标准溶液,用微孔滤膜(或滤纸)过滤沉淀。收集游液,用TI(Ⅰ)标准溶液滴定过量的四苯基硼离子。方法回收率为99.5％。测定结果与四苯硼化钾重量法结果一致。海水中共存离子不干扰测定,并可用于海水及多种盐溶液中钾的测定。本法因其简便、快速、准确而易于推广。