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.     

日本的海水化学资源提取技术研究

海水化学资源例如铀、锂提取技术已进入海水现场小规模试验。以纤维状偕胺肟类化合物为吸附材料 ,每公斤吸附剂的提铀量为 1 g。添加质量分数为 2 0 %聚氯乙烯的尖晶石型锰氧化物粒状海水提锂吸附剂 ,每克吸附剂的提铀量为 1 8mg。浮体式吸铀装置可用于深海作业。流动床或船舶提锂系统 ,可规模化海水提锂。吸锂剂的脱附以及脱锂液的浓缩分离已初步达到小型生产的程度。用吸附法从海水中提取的碳酸锂纯度达 99%以上 ,海水锂回收率为 2 7%。     

玻璃钛吸附剂的研制及其吸铀性能研究

本文报道一种机械强度高、吸铀性能较好的玻璃钛吸附剂的研制及吸铀性能研究。室内通水吸附剂回收率达99.4%,优于湿法制备的强度较好的水合氧化钛吸附剂。在铀浓度为lμg/ml时,铀的回收率平均为74.7%。铀在玻璃钛上的吸附是个吸热过程,吸附等温线显示两个平台,属分级交换模式。X射线衍射分析表明玻璃钛主要为无定形成分。     

Accumulation of uranium in sediments and phosphorites on the South West African shelf

Organic-rich sediments and coexisting phosphorites from the continental shelf off South West Africa have been analysed for uranium and thiorum by alpha-spectrometry. The uranium concentrations in the sediments range from 10 to 55 ppm, with an isotopic composition close to that of sea-water, indicating that uranium is passing into the sediments at the present time. The phosphorites occur in the sediments as thin unconsolidated laminae and as lithified nodules and pellets, with uranium contents ranging from 79 to 158 ppm. Based on the uranium isotopic composition, only the unconsolidated phosphorite laminae are recent, while the lithified nodules and pellets, with ²³⁴U/²³⁸U and ²³⁰Th/²³⁴U ratios close to radio-active equilibrium, appear to be inherited from a previous period of phosphorite deposition. Deposition of uranium appears to take place predominantly by incorporation into carbonate fluorapatite growing authigenically within the sediment. Uranium accumulation rates, computed from ¹⁴C-dated sections of the sediment cores, and using only uranium values with modern isotopic composition, range from 232 to 765 μg/cm² per 1,000 years. These results stress the importance of organic-rich sediments containing authigenic phosphorite beneath areas of high organic productivity as a major sink for uranium in the ocean.     

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.     

DETERMINATION FO URANIUM IN SEAWATER

This article deals with a new method of analysing in seawater, i. e. the uranium is concentrated with an aqueous suspension of basic zinc carbonate, subsequently isolated and determined by extraction-photometric method. In concentrating uranium such factors as stirring time, amount of adsorbent used, acidity of seawater were studied and conditions suitable for analysis were found. This method is simple, accurate and good in reproducibility. It is not necessary to adjust the pH of seawater before analysis. This technique can also be applied to determination of uranium in river or lake.     

AHP树脂水相成型及吸铀机理的探讨

应用有机吸附剂从海水中提取铀,资料上已有若干报道.Davies.R.J,等曾经报道过用甲醛、间苯二酚胂酸缩合的树脂,虽然这种树脂交换容量大(通水112天,1010微克铀/克),选择性好,提取率高,但它在水中缓慢水解,吸附能力下降,溶损也较大(2.3%初量/周),因而没有得到进一步的发展.Bayer,E.提出用聚乙二醛三氨基苯酚和经硅藻土烧结的聚丙烯氧肟酸树脂,从海水中提取铀和铜等金属,但吸附量不很高,树脂的强度也差,因此很快就中断了研究.苏联一些学者也报道了用AH、等阴离子交换树脂提取铀的研究工作.AH-2Φ树脂具有一定的吸附量(30微克铀/克),在海水中比较稳定,但交换容量很低,价格也较贵.     

Precipitation of authigenic uranium in suboxic continental margin sediments from the Okinawa Trough

Concentrations of U and Th isotopes in Okinawa Trough and East China Sea sediment cores were determined by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) to investigate the behavior of redox sensitive uranium in suboxic hemipelagic sediments and determine their significance in oceanic uranium balance. ²³⁸U concentrations and ²³⁸U/²³²Th activity ratios in the East China Sea sediments showed no remarkable variation with depth. However, ²³⁸U and ²³⁸U/²³²Th ratios in the Okinawa Trough sediments were low in the surface oxidizing layer but increased where the suboxic condition was encountered. The distribution profiles of ²³⁰Th and ²³²Th concentrations were relatively constant with depth in both the Okinawa Trough and East China Sea sediment cores. These results suggested that there has been post-depositional precipitation of authigenic uranium within the suboxic Okinawa Trough sediment column. The post-depositional precipitation rates of authigenic uranium were estimated to be 47 ± 5 to >62 ± 8 ng cm⁻² yr⁻¹; these rates were comparable to those previously reported for several anoxic sediments. A mechanism controlling precipitation of uranium may be the downward diffusion of uranium U(VI), reduction to U(IV) and finally precipitation onto the solid phase. The accumulation rate of uranium for the Okinawa Trough sediments was approximately eight times higher than the world average rate reported for suboxic sediments. This removal of uranium in the oceanic budget increases the importance of the suboxic sediment sink.     

Uranium in rivers and estuaries of globally diverse, smaller watersheds

Data for uranium concentrations in 29 rivers and eight estuaries are presented. The river data expands the existing database on riverine uranium transport to include more smaller watersheds which collectively account for a large portion of material transport from the continent to the oceans. Riverine concentrations for these smaller watershed range from less than 50 to 660 pM. The results for these systems, when combined with previously published data on mostly larger rivers, do not change significantly the calculated global riverine flux and thus earlier estimates by Palmer and Edmond [Palmer, M.R., Edmond, J.M., 1993. Uranium in river water. Geochim. Cosmochim. Acta, 57, pp. 4947–4955] are substantiated. Uranium transport through eight diverse estuaries was studied to assess the importance of estuarine removal in the global marine uranium budget. Results indicate that uranium is conservatively transported in most systems studied. Results reported here for the Savannah estuary, however, indicate significant uranium removal. Our results suggest that uranium is removed in salt marsh estuaries at a rate of ca. 70 μmol/m². This compares to a rate of 15 μmol/m² for Delaware salt marshes [Church, T.M., Sarin, M.M., Fleisher, M.Q., Ferchlman, T.G., 1996. Salt marshes: an important sink for dissolved uranium. Geochim. Cosmochim. Acta, 60, pp. 3879–3887]. We suggest that uranium removal to salt marsh sediments is due to anaerobic microbially mediated processes. We use these results to estimate the global significance of the salt marsh sink in the oceanic budget of uranium. We estimate that 2.7×10⁷ mol of uranium are removed to salt marshes annually as compared to an annual global riverine input of 3–6×10⁷ mol estimated by Palmer and Edmond [Palmer, M.R., Edmond, J.M., 1993. Uranium in river water. Geochim. Cosmochim. Acta, 57, pp. 4947–4955].     

Dissolved uranium in the Baltic Sea

Filtered water from the Baltic Sea was analysed for uranium concentration and ²³⁴U/²³⁸U activity ratio with alpha-ray spectrometry. The uranium concentration shows a strong correlation to salinity, the correlation coefficient being close to 0.98. Consequently, the uranium concentration increases from 0.15 μg kg⁻¹ in the northern part, dominated by fresh water, to above 1.0 μg kg⁻¹ in the Belt Sea. However, the data also show that dissolved uranium is not strictly conservative in the Baltic. In deeper intermittently anoxic basins of the Baltic Proper, the element is removed from the water phase and incorporated into the sediment. This is most evident in the Gotland Deep, which has been anoxic below 200 m depth since 1979.     

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.     

Adsorption of lead and cadmium ions on calcite in the Krka estuary

The adsorption of Pb²⁺ and of Cd²⁺ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO₃, Merck p.a.) was investigated. Simultaneous adsorption of Pb²⁺ and Cd²⁺ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb²⁺ remained firmly bound to calcite at all salinities, whereas Cd²⁺ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd²⁺. The experiments were performed at metal concentrations of 8 × 10⁻⁸ mol l⁻¹ and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (K_d) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.     

The coprecipitation of uranium with calcium carbonate

This report is one of the studies on the factors controlling the trace element contents of marine calcareous skeletons. The values of the distribution coefficients of UO₂ ²⁺ between solutions and carbonate precipitates were measured in the laboratory at 20±1C. From the determination of the uranium contents of marine calcareous skeletons and sea water, the values of uranium between marine calcareous skeletons and sea water are expected as 1.2 to 0.3 for aragonite and 0.2 to 0,0n for calcite. The experimentally measured value of the distribution coefficient for aragonite is thermodynamically discussed. And it was known that the value of the distribution coefficient of UO₂ ²⁺ is controlled greatly by the activity coefficient of uranium dissolved in a parent medium and the crystal form of CaCO₃. The activity coefficient of uranium in solution mainly owes to the formation of complexes between UO₂ ²⁺ and CO₃ ^2–in the solution.     

九龙江河口区表层水铀同位素的粒级分布

利用微滤和超滤技术研究了九龙江河口区表层水中铀及其同位素组成的粒级分布和地球化学行为.结果表明,溶解态(<0.4μm)中低分子量组分(<10 000 u)占主要份额,胶体态(10 000 u~0.4μm)238U所占比例不足1%,且随盐度的增加其所占份额逐渐降低.溶解态、低分子量组分和胶体态238U的比活度与盐度之间存在良好的线性正相关关系,证实它们在九龙江河口区呈现保守行为.在颗粒态(>0.4μm)中,各粒级组分238U所占份额主要受控于相应颗粒物的浓度,在盐度小于20的区域,各粒级颗粒组分238U占颗粒态的份额有如下变化次序:10~53μm>2~10μm>0.4~2μm>大于53μm,而在盐度大于30的近外海站位,该次序发生一些变化:0.4~2μm>10~53μm>2~10μm>大于53μm,最小粒级颗粒组分238U的贡献有所增加,反映了自生铀贡献的加强.九龙江河口区表层水中溶解态(包括低分子量组分和胶体态)的234U/238U)_A.R.均大于1,显示出234U过剩的特征,而各粒级颗粒组分中的234U/238U)_A.R.则接近于平衡值(1.0).这一现象与陆地岩石风化过程中水体对铀的淋滤释出量及234U的优先浸出有关.对232Th/238U质量比的研究显示,溶解态及其所包括的低分子量组分和胶体态的232Th/238U质量比均小于1,而颗粒态及其所包括的4个粒级组分中的232Th/238U质量比均大于1,反映了向外海输送过程中铀、钍地球化学行为的差异.     

悬浮泥沙在长江口铀非保守行为中的重要作用

利用高精度的电感耦合等离子体质谱仪对2014年1月长江口表层水中溶解铀浓度及其234U/238U比值、2013年3月长江口表层沉积物中各矿物组分的铀含量及其234U/238U比值进行了测定,研究了其空间分布特征和影响因素。结果表明:除了长江径流和海水之外,长江口还有其他的溶解铀来源。水体中过剩铀与悬浮颗粒物浓度呈现显著相关性（r2=0.96）。对长江口表层沉积物进行的序列提取实验进一步表明,水体中悬浮颗粒物或沉积物中可解吸态和碳酸钙结合态铀可以在河口区域释放进入水体,而铁锰氧化物和有机物结合铀比较稳定,不受河口区混合过程的影响。每千克颗粒物或沉积物能够释放约2 μmol颗粒态铀,使其转化为溶解态。然而,铁氢氧化物和细颗粒物的絮凝吸附作用也可使溶解铀同时从河口水体中清除。在低盐度区,铀的清除和添加过程速率相近,使溶解铀呈现暂时的"伪保守"现象:颗粒态释放的铀具有明显低的234U/238U比值,导致水体的234U/238U低于保守混合值。在中高盐度区域,溶解铀呈现明显的富集现象。但是由于水相和颗粒相中的铀交换,可释放颗粒态铀的234U/238U接近溶解铀的234U/238U比值,从而导致水体的234U/238U比值呈现出保守性。长江口颗粒物的铀释放通量为（3.48±0.41）×105 mol/a,约占输入的总颗粒态铀通量（1.80±0.17）×106 mol/a的19.3%。长江口输入东海的溶解铀总通量（河流溶解态铀与河口添加铀之和）为（2.68±0.13）×106 mol/a,约为世界河流入海铀通量的11.7%。     

The uranium content and the activity ratio234U/238U in marine organisms and sea water in the western North Pacific

The uranium content and activity ratio A²³⁴U/A²³⁸U were determined in open ocean water, marine plankton, marine algae and sea water in the environment in which plankton and algae live. The average uranium content of 3.34±0.28×10⁻⁶ g/l and the average activity ratio of 1.13±0.04 were obtained in open ocean water. The uranium contents in plankton and algae were respectively from 1.7 to 7.8×10⁻⁷ g/g and 0.4 to 23.5×10⁻⁷ g/g on dry basis with the respective concentration factors of 48 to 260 and 10 to 733. The activity ratio in plankton and algae ranged from 1.07 to 1.18 which coincided well with those in the environmental sea water.     

Behavior of uranium in two estuaries of the southeastern United States

Soluble uranium concentrations in the Ogeechee and Savannah Rivers are 0.046 ± 0.005 and 0.026 ± 0.01 μg/l, respectively. Particulate concentrations are approximately similar in the Ogeechee River but are about four times the soluble concentration in the Savannah River. River end-member ²³⁴U/²³⁸U ratios range from 1.04 ± 0.04 to 1.08 ± 0.12. Observations suggest that uranium is removed from estuarine waters at low salinities during low discharge.     

Thorium speciation in seawater

Since the 1960s, thorium isotopes occupy a special place in the oceanographer's toolbox as tracers for determining rates and mechanisms of oceanic scavenging, particle dynamics, and carbon fluxes. Due to their unique and constant production rates from soluble parent nuclides of uranium and radium, their disequilibrium can be used to calculate rates and time scales of sinking particles. In addition, by ratio-ing particulate ²³⁴Th (as well, in principle, other Th-nuclides) to carbon (and other elements), and linking this ratio to the parent–daughter disequilibrium in the water column, it is possible to calculate fluxes of carbon and other elements. Most of these applications are possible with little knowledge of the dissolved chemical properties of thorium, other than its oxidation state (IV) and tendency to strongly sorb to surfaces, i.e., its “particle- or surface-activity”. However, the use of any tracer is hindered by a lack of knowledge of its chemical properties. Recent observations in the variability of carbon to ²³⁴Th ratios in different particle types, as well as of associations of Th(IV) with various marine organic biomolecules has led to the need for a review of current knowledge and what future endeavors should be taken to understand the marine chemistry of thorium.     

不平衡铀系和钍系核素的γ谱测定

求解初始时刻子体活度不为零时两个子体级连衰变动力学方程,给出γ谱分析测量不平衡铀系和钍系核素活度的计算公式.作为应用测量了两个沉积物样品中的238U,234Th,226Ra,222Rn,228Ra,228Th,224Ra,212Pb,210Pb和40K的活度.     

偕胺肟基聚丙烯腈/蒙脱土纳米复合材料海水铀的吸附规律研究

采用偕胺肟化聚丙烯腈/蒙脱土(APAN/MMT)复合纳米吸附材料对海水中的铀进行吸附,考察了吸附条件对APAN/MMT吸附铀量的影响,并对APAN/MMT吸附铀的动力学和热力学进行了探讨.结果表明:铀初始浓度、溶液温度较高、采用磁力搅拌吸附方式有利于吸附速率的提高,溶液pH对吸附性能有一定的影响,在pH为5时,平衡吸附...