Mechanisms of enrichment of the rarer elements in marine manganese nodules

The rare-earth distribution has been determined in five manganese nodules from a range of marine environments. Manganese nodules from Loch Fyne, Scotland, and the Gulf of Aden are characterized by a low absolute abundance of the rare-earth elements and a low Ce/La ratio compared with deep-sea nodules. This difference is interpreted in terms of the diagenetic remobilization of manganese in the high sedimentation regimes leading to the effective fractionation of manganese from the rare-earth elements and the resultant depletion of the rare earths in nodules from these environments. The mechanism of incorporation of the rare-earth elements into manganese nodules is thought to be either the direct adsorption of these elements from seawater or the scavenging of the elements by colloidal iron oxide prior to their incorporation into the authigenic phase of nodules. There appears to be no evidence for the surface transfer of these elements from inorganic detritus into the authigenic phase of nodules as suggested by previous authors. The distribution of U and Th in the nodules is controlled by factors similar to those controlling the rare-earth abundance in nodules. The higher U/Th ratios in nodules from Loch Fyne and the Gulf of Aden is considered to be due to the preferential reduction of UO₂(CO₃)₃^4? to some lower-valency uranium species such as U₃O₈ in nodules from less oxidizing environments.     

Radiochemical studies of deep-sea manganese nodules

Five manganese nodules collected from the Northern Mid - Pacific have been analysed for their U and Th isotopes.lt is found that the enrichment of thorium compared to uranium is universal in deep- sea manganese, nodules and in the top sides of the nodules there are large excesses of Th and Pa decreasing exponentially with depth. For each of the nodules, the concordant growth rates are obtained from three different methods: 230Thex 230Thex/232Th and 231Paex.The growth rates of manganese nodules are closely related to the chemical compositions of the nodules and the types of the underlying sediments. The growth rates of five nodules are determined to be in the range of 0.79-7.4 mm/106a, in agreement with those predicted from the chemical compositions of the nodules. By the comparison of the extrapolated 230Thex,230Thex/232 Th and 231PaeX data from the top and bottom surfaces of the nodule from Site M21 yields, the nodule turnover time is (9.83-13.7)×104a.     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

SIMULTANEOUS DETERMINATION OF TRACES OF URANIUM AND THORIUM IN SEAWATER BY ISOTOPE DILUTION MASS SPECTRO-METRIC ANALYSIS METHOD(IDMS)

The separation and simultaneous determination of the traces of U and Th in seawater by IDMS is described. The detection limits of this method are 2.4×10-9 g for Th and 1.1×10-8 g for U. The concentrations of U and Th in seawater nearby Xiamen were measured, which are 3.20 ppb and 7.73 ppt respectively. The precisions fo the method are ±1.7% for U and ±3.6% for Th respectively.     

海洋样品中~(231)Pa和U,Th同位素的联合分离测定

本文结合已报道的U,Th分离方法和~(231)Pa分离条件建立了Th-Pa-U联合分离流程和测试技术,并用以分离测定一个锰结核和一个深海沉积物样品中的~(231)Pa,U和Th同位素含量的深度分布。用~(231)pa_(ex),~(230)Th_(ex)和~(230)Th_(ex)/~(232)Th法分别计算该锰结核的生长速率为1.5,0.9和1.5mm/Ma。U,Th和~(231)Pa的化学回收率(％)分别为40—80,80—92和60—86。     

Study on the manganese nodule V. Thermal studies of the iron-manganese phase

The thermal phase transformation of the iron-manganese phase of the Pacific Ocean manganese nodules were studied by the differential thermal and X-ray diffraction methods. X-ray powder patterns of the heated samples at the temperature of 600°C to 1000°C show the occurrence of hematite, bixbyite and cubic and tetragonal (Fe, Mn)₃O₄. Bixbyite produced by the heat treatment of the iron-manganese phase gives an abnormal X-ray pattern in comparison with the standard sample of bixbyite. Cubic (Fe, Mn)₃O₄ is produced not only by the reaction of bixbyite with hematite over 900°C, but also at the lower temperature, such as 600°C. While, tetragonal (Fe, Mn)₃O₄ is a reaction product of cubic (Fe, Mn)₃O₄ with bixbyite over 900°C in the case of manganese rich nodules. The species and quantities of the products after the heat treatment are assumed to be mostly influenced by the relative contents of iron and manganese in the manganese nodule.     

Study on the managanese nodule

Chemical and X-ray analyses were performed on the fifteen manganese nodules collected from the Pacific Ocean floor. The results were discussed compared with the previous data on the manganese nodules. Minerals were found to be todorokite, δ-MnO₂ and other silicates, montmorillonite, illite, phillipsite and α-SiO₂. Average composition shows that copper is concentrated on the deep sea nodules more than the shallow ones, and that the todorokite rich nodules contain more copper and nickel than the δ-MnO₂ rich ones. The analyses of fresh water iron-manganese precipitates by bacterial activity suggest that biological process is one of the important factors on the genesis of the sedimentary iron-manganese deposits, including the manganese nodule. The Institute of Physical and Chemical Research     

铀、钍在碳酸钙-海水界面的附着行为研究

运用实验模拟的手段,对铀(U)、钍(Th)在碳酸钙-海水界面的附着行为进行了初步研究,通过测定相关的分异系数(D)定量评估了文石和方解石两种碳酸钙矿物对U和Th的捕集作用。实验结果显示,不仅U和Th之间存在显著差异,而且两种碳酸钙矿物之间也存在明显不同。U介于碳酸钙和海水之间的分异系数(DU)分别在1.5~3.5(文石)和0.04~0.19(方解石)区间内变化,分异行为非常微弱但其分异系数随着碳酸钙沉淀速率的增加而逐渐上升。这表明U元素主要是以共沉淀的方式进入到文石或方解石沉淀中,但由于其在海水溶液中主要以2 22 3UO(CO)nn的形式存在,因而只能以占据晶格缺陷的方式进入碳酸钙。与之相反的是,文石和方解石都对Th表现出极强的捕集能力,所测定的分异系数(DTh)分别在240~6 330(文石)和430~6 160(方解石)范围内变化,但DTh与碳酸钙沉淀速率之间无明显关联。Th在碳酸钙表面的附着行为可界定为单纯的吸附作用,这一行为应与Th主要以Th(OH)4的形式赋存于溶液中有关。     

两个大洋多金属结核标准物质中27种元素的等离子体质谱法测定

从样品制备、仪器操作参数最佳化、内标补偿等几方面着手,利用两个标准物质(GSPN-2,GSPN-3)发展了大洋多金属结核中27种元素的等离子体质谱(ICP-MS)测定方法.这27种元素包括Ba,Ce,Co,Cu,Dy,Er,Eu,Gd,Ho,La,Li,Lu,Mo,Nd,Pr,Sb,Sc,Sm,Tb,Th,Tm,U,V,W,Y,Yb和Zn.各元素测定值与保证值相当吻合.对GSPN-2和GSPN-3,Ba,Sb,Sc,Y,Zn等5种元素可用外标校准法准确测定,其平均回收率(n=3)在91.4%～106.9%之间;可用内标(103Rh)校准法准确测定其他22种元素,其平均回收率(n=3)在89.4%～110.2%之间;各元素3次测定的相对标准偏差(RSD)为0.0%～11.0%.     

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.     

锰结核生长的古海洋环境与事件

本文通过东太平洋海盆、中太平洋海盆锰结核、云南东南部土壤锰结核及原生沉积锰矿特征及形成环境的对比研究,表明:(1)海洋水深,地形、生物生产力与水—沉积物界面的Eh、pH值等是控制锰结核物质成份、生长速率及分布格局的重要因素,(2)南极底层流和深海沉积间断的形成发展是造成锰结核生长间断的关键,(3)新生代低海平面时期可能是锰结核生成的重要时期。     

西太平洋某海域锰结核的矿物学及矿物化学研究

锰结核中的矿物是对结核生长环境反映。对结核进行X射线衍射分析表明:结核中锰矿物主要为水羟锰矿,并含有石英、钙十字沸石、斜长石、以及绿脱石、辉石、方解石和少量的蒙脱石、伊利石、角闪石、绿泥石、白云石、锐钛矿等。锰矿物表明该区为氧化环境,且受到火山、热液活动的影响。定量分析结果表明结核各矿物的含量变化很大,说明结核的生长过程中环境发生了变化。电子探针分析结果表明:结核锰矿物的组分含量变化较大,表明结核的元素来源的不稳定性。     

UTEVA树脂分离纯化珊瑚中铀、钍的改进研究

珊瑚是记录海洋环境变化信息的载体之一,测定其U/Ca比值可重建海水温度或测定Th/U同位素比值可计算年龄重建海平面高度等.准确测定珊瑚中U、Th含量及同位素比值是提取所记载的海洋环境变化信息的前提,其难点在于高Ca基体分离和痕量U、Th富集纯化.基于此,本研究拟采用UTEVA树脂改进了一步富集分离珊瑚中U、Th的前处理...     

太平洋北部锰结核区沉积物中Fe,Mn,Al和CaCO3的含量分布特征

1985年12月至1986年4月对西太平洋锰结核进行了调查并对所获沉积物样品进行了分析,研完了锰结核区域沉积物中Fe,Mn,Al和CaCO_3的含量分布特征及其相关关系,说明沉积物中Fe,Mn,Al和caCO_3的含量分布特征主要受水深的制约。     

Composition and Useful Properties of Tailings of Marine Manganese Nodules and Crusts

ABSTRACT

Marine manganese nodules and crusts, when processed, yield tailings which may be utilized for environmental and economic benefit. The key to the reasonable and effective utilization of these tailings lies in making a systematic appraisal of their composition and properties. This article gives an introduction to the investigation of manganese tailings properties. The tailings have a high iron and/or manganese content, high surface area, high porosity, and fine grain size. Some tailings have a high rare earth element content which is valuable. They may also have high SO₃, arsenic, and uranium contents which are harmful. Depending on the process used to produce the tailings, there will likely be some differences in chemical composition, mineral assemblages, surface area and adsorption capability, pore diameter and volume, density and pH. In assigning potentially beneficial applications for these tailings, these differences should be taken into account to optimize utilization.     

Organic material accumulation of Carnian mudstones in the North Qiangtang Depression,eastern Tethys: Controlled by the paleoclimate,paleoenvironment, and provenance

The Late Triassic mudstones are considered to be the most significant hydrocarbon source rocks (TOC: 0.54%–3.29%) in the North Qiangtang Depression, eastern Tethys. Here, we present geochemical data from the Woruo Mountain Carnian mudstones, in order to investigate their paleoclimate, paleoenvironment, and provenance and to analyze the mechanism of organic material accumulation. The paleoclimate condition was warm and humid during the Carnian mudstones deposition, as indicated by moderate chemical index of alteration (CIA; 73–76), which may be connected with the Late Triassic Carnian stage global climate event in the Tethys. The low U/Th (0.17–0.25) and C_org/P_tot (7–33) ratio values and moderate manganese contents, reflect the oxidizing conditions during the Carnian mudstones deposition. The relatively high primary productivity in this study is supported by the relatively high P concentrations. The Al₂O₃–(CaO* + Na₂O)–K₂O ternary plot and Th/Sc–Zr/Sc crossplot reflect that the source areas have undergone a medium chemical weathering with weak sedimentary recycling. The TiO₂–Zr, Co/Th–La/Sc, La/Th–Hf, and La/Yb–∑REE bivariate diagrams indicate that the provenance of Carnian mudstones was primarily from felsic igneous rocks. The collision setting has been identified based on the multi-major elements discriminate plots in the present study. The Riwanchaka and Mayigangri masses to the southwest and south of the study area consisting mainly of Middle-Triassic granodiorite and Late-Triassic granite are likely responsible for supplying provenance to the Woruo Mountain Carnian mudstones, which have similar REE patterns. The relatively high TOC contents of Carnian mudstones are related to high paleoproductivity and fast sedimentation rates, which will lead to preservation of some organic matter even when bottom waters are completely oxidizing. The detrital input during the Carnian mudstones deposition would result in dilution of organic matter.     

Last glacial emplacement of methane-derived authigenic carbonates in the Sea of Japan constrained by diatom assemblage,carbon-14, and carbonate content

We studied diatom assemblages and CaCO₃ contents of methane-derived authigenic carbonates from the eastern margin of the Sea of Japan and assessed the formation time of these samples. Radioactive ¹⁴C date was determined in selected samples to obtain the maximum age of the time. The results of our study suggest mass formation of carbonate nodules in a glacial period within ∼40 ky, consistent with a published U/Th dating result of carbonate nodules in the study area. Diatom assemblages and contents in the carbonate nodules (abundance of ∼10⁶/g, dominance of neritic-littoral species, warm/cold water species ratio lower than ∼25) differ from the near-seafloor sediments in the study area, which have characteristics of Holocene sediments in the Sea of Japan, and suggest cementation of glacial sediments. Laminated sediments in some nodule samples are glacial sediments because laminations are records of a low sea level period in the semi-enclosed ocean. Similarity of diatom assemblages and contents in all carbonate samples is another evidence of glacial sediments in nodules. Glacial sediments with oceanic cold water species as low as Holocene sediments restricts the sediment age to before 20 cal. ky BP. Carbonate contents higher than 78 wt% suggest the cementation of poorly compacted sediments near the seafloor, and the date of carbonate cementation is, therefore, close to that of the cemented sediments. Most carbonate nodule samples in this study were formed in a glacial period and detection of ¹⁴C restricts this period to within ∼40 ky.     

黄河下游及河口区表层沉积物中U,Ra,Th,40K和137Cs的测定

本文从地球化学和环境保护的角度,用8180—4Kγ谱仪直接测定方法确定了天然放射性元素U,Ra,Th,~(40)K,及人工核素~(137)Cs的含量,讨论了它们的分布特点及其影响因素,指出了河口区与下游段元素变化的差异及其制约条件。     

Growth conditions of manganese nodules comparative studies of growth rate, magnetization, chemical composition and internal structure

Twenty-four manganese nodules from the surface of the sea floor and fifteen buried nodules were studied. With three exceptions, the nodules were collected from the area covered by Valdivia Cruise VA 04 some 1200 nautical miles southeast of Hawaii.Age determinations were made using the ionium method. In order to get a true reproduction of the activity distribution in the nodules, they were cut in half and placed for one month on nuclear emulsion plates to determine the α-activity of the ionium and its daughter products. Special methods of counting the α-tracks resolution to depth intervals of 0.125 mm. For the first time it was possible to resolve zones of rapid growth (impulse growth) with growth rates, s > 50 mm/10⁶ yr and interruptions in growth. With few exceptions the average rate of growth of all nodules was surprisingly uniform at 4–9 mm/¹⁰ yr. No growth could be recognized radioactively in the buried nodules. One exceptional nodule has had recent impulse growth and, in the material formed, the ionium is not yet in equilibrium with its daughter products. Individual layers in one nodule from the Indian Ocean could be dated and an average time interval of t = 2600±400 yr was necessary to form one layer. The alternation between iron and manganese-rich parts of the nodules was made visible by colour differences resulting from special treatment of cut surfaces with HCl vapour. The zones of slow growth of one nodule are relatively enriched in iron.Earlier attempts to find paleomagnetic reversals in manganese nodules have been continued. Despite considerable improvement in areal resolution, reversals were not detected in the nodules studied. Comparisons of the surface structure, microstructure in section and the radiometric dating show that there are erosion surfaces and growth surfaces on the outer surfaces of the manganese nodules. The formation of cracks in the nodules was studied in particular. The model of age-dependent nodule shrinkage and cracking surprisingly indicates that the nodules break after exceeding a certain age and/or size. Consequently, the breaking apart of manganese nodules is a continuous process not of catastrophic or discontinuous origin. The microstructure of the nodules exhibits differences in the mechanism of accretion and accretion rate of material, shortly referred to as accretion form. Thus non-directional growth inside the nodules as well as a directional growth may be observed. Those nodules with large accretion forms have grown faster than smaller ones. Consequently, parallel layers indicate slow growth. The upper surfaces of the nodules, protruding into the bottom water appear to be more prone to growth disturbances than the lower surfaces, immersed in the sediment. Features of some nodules show, that as they develop, they neither turned nor rolled. Yet unknown is the mechanism that keeps the nodules at the surface during continuous sedimentation. All in all, the nodules remain the objects of their own distinctive problems. The hope of using them as a kind of history book still seems to be very remote.