Uptake of platinum group elements by the marine macroalga, Ulva lactuca

Uptake of environmentally relevant platinum group elements (PGE) by the marine macroalga, Ulva lactuca, has been studied. Removal of nM concentrations of Rh(III), Pd(II) and Pt(IV) added to filtered sea water appeared to proceed via pseudo-first-order kinetics, with respective forward rate constants of either 0.0039 or 0.0042 h^− 1, 0.0058 or 0.0096 h^− 1 and 0.0017 or 0.0032 h^− 1, depending on whether an irreversible or reversible reaction was invoked. The (quasi-) equilibrium distribution coefficients, derived from linear fits to uptake (sorption) isotherms, were about 1400, 900 and 350 mL g^− 1 on a dry mass basis for Rh, Pd and Pt, respectively. With increasing sea water pH, over the range 7.9 to 8.4, uptake of Rh by Ulva increased considerably, whereas a small increase in Pt removal was observed; in contrast, uptake of Pd exhibited no clear dependence on pH. The percentage of metal taken up that was internalised within cells, evaluated by washing selected algal samples in 3 mM EDTA, was about 40% for Rh, 80% for Pd and 95% for Pt. Results of this study were interpreted in terms of what is known about the aqueous speciation of PGE in sea water. Thus, Rh exists as cationic hydrated chloride complexes which are readily adsorbed at the algal surface. Palladium has an exceptional affinity for organic ligands, and uptake (and internalisation) appears to be governed by competition for Pd²⁺ from aqueous and algal binding sites. Platinum (IV) exists predominantly as a series of (mainly) negatively charged chloride and mixed hydroxychloride complexes that have little propensity to interact with the algal surface; however, its high degree of internalisation requires at least some interaction with specific and perhaps physiologically active sites.     

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%.     

Particle–water interactions of platinum group elements under estuarine conditions

Particle–water interactions of selected platinum group elements (PGE) have been studied as a function of pH (between 5 and 10), salinity, and concentrations of Cl⁻ and Ca²⁺. Rhodium(III), Pd(II) and Pt(IV) were added to water samples and sediment suspensions and, following a period of equilibration and subsequent phase separation, filtrates and HCl-digested filters were analysed by ICP-MS. PGE removal from the aqueous phase to the particulate phase appeared to proceed via both coagulation of organic/colloidal associations and adsorption to estuarine sediment particles. In river water, removal of Rh increased and Pt decreased with increasing pH, whereas Pd was not detected in the particulate phase throughout much of the pH range studied. In end-member estuarine water (salinity = 28), removal of Rh and Pt increased with increasing pH, but removal of Pd was relatively insensitive to pH. Conditional particulate-aqueous distribution coefficients, K_Ds (mL g^− 1), were on the order of a few hundred (Pd and Pt) to several thousand (Rh) along the estuarine gradient. Increasing salinity and Cl⁻ concentration were accompanied by an increase in K_D for Rh and Pd, and a reduction in K_D for Pt, while increasing Ca²⁺ concentration resulted in an increase in K_D for all PGE. Experimental observations were qualitatively interpreted in terms of what is known about the aqueous speciation of PGE. Thus, Rh data were consistent with the adsorption of cationic species of the form: [RhCl_6−x(H₂O)_x]^x−3, where x = 0 to 6; although in river water complexation by additional (e.g. organic) ligands may have also occurred. Speciation of Pd was predicted to be dominated by organic complexes under all experimental conditions, consistent with its stabilisation in solution in freshwater and apparent salting out and/or coagulation in the presence of dissolved ions. The presence of hydroxychloride complexes of Pt(IV), whose ligand number (and negative charge) increases with increasing chlorinity, could explain most of the experimental observations for this element.     

Occurrence forms and distribution of precious and base metals in ferromanganese crusts from the Sea of Japan

The examination of polished sections of ferromanganese crusts from the Sea of Japan revealed abundant inclusions of small grains of base and precious metals: Ag, Pd, Pt, Au, Rh, Cu, Zn, Sn, P, Ni, Cr, Ti, Sb, As, W, and Mo. The metals occur in the form of native elements or intermetallic compounds, subordinate sulfides, sulfates, oxides, tungstates, and phosphides. The data on contents, occurrence forms, and distribution of these metals in the ore crusts from this region are discussed.     

Structural, curvature and electronic properties of Rh adsorption on armchair single-walled carbon nanotube

This paper systematically studies the rolling effects of the (n, n) single-wall carbon nanotubes (SWCNT) with different curvatures on Rh adsorption behaviours by using density functional theory. The outside charge densities of SWCNTs are found to be higher than those inside, and the differences decrease with the increase of the tube radius. This electronic property led to the discovery that the outside adsorption energies are higher than the inside ones, and that the differences are reduced with the increase of the tube radius. Partial density of states and charge density difference indicate that these strong interactions induce electron transfer between Rh atoms and SWCNTs.     

西沙群岛生物碳酸盐的成因和沉积:来自活体仙掌藻的证据

A recent island survey reveals that the Xuande Atoll and the Yongle Atoll in the Xisha Islands can be classified into one of two systems: the depleted atoll system and growth atoll system; the survey also indicates that the decreased area of several shoals is an unbearable burden for the Xisha Islands, of which the largest island area is 2.13 km2 and the minimum elevation is 1.4 m. According to a survey on the ecological characteristics of Halimeda in the Laolongtou breaker zone of Shidao Island in the Xisha Islands, the green and white living Halimeda are collected,the isotopic ages of 14 C contained in the Halimeda are shown to be 27 years and 55 years, respectively, and carbonate mainly occurs in five types, i.e., luster, segment, sand, sand grain, and marl in the formation. The Halimeda segments mainly provide the carbonate sediments of long-term biogenic deposits in the reef environment and the annual productivity per area is 60–100 g/m2; the characteristics of the microstructure of the Halimeda are analyzed, the aragonite raphide carbonate is deposited and enriched in the cortexes, medullas and cysts, and the Halimeda generally contain major elements such as C, O, Ca, Cl, Mg, K, Na, S and Al, and are rich in trace elements such as tellurium(Te), rhodium(Rh) and strontium. It is believed that the Halimeda grow slowly,including the biotic community of reef corals in the reef areas, thus they possess an environmental remediation capacity, but it takes much time to remedy the environment, and it is necessary to make the law to protect the diversity and vulnerability of the Xisha marine ecology, the ecology of the reef community and the island environment in a scientific way. As indicated in the survey, under the background of global warming and sea-level rise, the discovery of large amounts of Halimeda in the Laolongtou sea area is significant for the natural increase of the depleted atoll system of the Xuande Atoll, while the Halimeda segments represent the primary form of the fossil Halimeda, of which the species can be identified and preserved in great numbers under geological conditions. The Miocene was discovered in large amounts in the Xichen-1 well, therefore the study on the characteristics and mechanism of Halimeda carbonate sediments plays a pivotal role in the formation and construction of organic reefs in the South China Sea as well as oil and gas exploration.     

A SIMPLE MODEL OF ELEMENT BALANCE IN ESTUARY

A simple one-dimensional mathematic model is presented to discuss the balance and behavior of elements in estuary system. The results are as follows: (1) Besides chemical and biological factors, the remo\-al of non-conservative elements is closely concerned with physical processes. (2) When the behavior and balance of non-conservative elements are studied, the mean residence time of these elements is a useful parameter, which can be obtained by combining the information from field-observation with mathematical model. (3) Based on different situations in estuary, the sensitivity and accuracy of the analytical method used must be considered in the study of the removal of such elements.     

海洋沉积物/颗粒物在生源要素循环中的作用及生态学功能

海洋沉积物/颗粒物是生源要素循环过程中的关键源与汇,沉积物/颗粒物一方面是海水生源要素的主要归宿,生源要素从溶解态经复杂的生物-化学过程转变为颗粒态,颗粒物质再沉降形成沉积物,另一方面,海洋沉积物/颗粒物经过微生物-浮游动物-底栖生物作用分解形成溶解态的生源要素,并释放到海水中再次被浮游植物利用,进入下一轮循环,所以,海洋沉积物/颗粒物具有异常重要的生态学功能。浮游植物是海水溶解态生源要素的利用者和海源颗粒态生源要素的初始形成者,浮游动物通过摄食浮游植物或其他有机颗粒物可释放出溶解态生源要素或形成更大的颗粒物,颗粒物沉降后形成的沉积物又通过底栖生物摄食-扰动-破碎等过程将颗粒生源要素释放进入水体参与再循环。生态系统不同类群的生物在颗粒生源要素的释放-沉降中所起的作用不同而又相互关联,其中浮游动物-底栖生物的摄食与代谢、微生物参与的分解过程起着非常重要的作用。所以,海洋沉积物/颗粒物生态学功能研究作为支撑海洋环境和资源的持续利用的科学基础,已成为海洋科学的前沿领域,必将获得跨越发展。     

南黄海西部陆架区表层沉积物稀土元素及其物源分析

对南黄海西部陆架区486个表层沉积物样品的稀土元素进行了测试分析。结果表明:稀土元素总量分布特征受粒度影响,其含量总体上随平均粒径的减小而升高,但在局部站位其含量还可能受矿物控制。稀土元素相关参数,如轻重稀土元素分异度、铈异常以及铕异常基本不受粒度影响,而主要受源岩组分控制,可以进行有效的物源判别。研究区不同站位沉积物中稀土元素配分曲线均为右倾的负斜率模式,相对富集轻稀土元素,显示中等程度的铕负异常,无明显铈异常。稀土元素相关参数物源判别表明研究区物质主要来源于黄河。     

Mesoscale modeling of water penetration into concrete by capillary absorption

Water penetration into concrete by capillary absorption plays a very important role in the ingress of contaminative substances when the structures are built in aggressive environments. In the present paper the lattice network model is proposed based on the unsaturated flow theory to predict the water penetration into concrete. On the mesocale level, concrete is treated as a three-phase composite. By means of the Voronoi diagram meshing strategy, the lattice network model of concrete with different types of lattice elements is developed. The corresponding transport properties are assigned to the lattice elements in the network falling in different phases. As a result, the lattice elements are idealized as conductive “pipes” in which uni-directional flow can be realized between the two nodes of the elements. Parameters in the lattice network model, such as the sorptivity and porosity of the mortar and the ITZs are quantitatively determined. With help of the approach, the water content distribution within a concrete sample after any elapsed time, especially the penetration depth of water frontier, can be easily predicted. The cumulative water absorption calculated by the lattice network model is shown to be well agreed with the experimental results.     

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.     

大沽河流域地下水中稀土元素的地球化学特征

近岸地下水排泄是近海稀土元素的重要来源,目前对地下水中稀土元素的地球化学行为的认识还十分有限。本文通过现场调查和模拟计算对山东大沽河流域地下水中溶解态稀土元素的分布、影响因素及络合形态进行了研究。结果表明：稀土元素在地下水中的分布具有较大的空间差异,pH和铁锰氧化物/氢氧化物的还原性溶解是影响稀土元素含量的重要因素。稀土元素的络合形态以LnCO+3和Ln(CO3)-2为主,但是在硫酸根含量较高的情况下,轻稀土较中稀土和重稀土更易于形成LnSO+4。大沽河流域地下水表现为重稀土富集,含水层中负电荷颗粒物对LnCO+3的优先吸附可能是富集的原因。受周边炼油厂影响,所有样品中的La均表现为正异常,人为源La在地下淡水和再循环海水中所占比例分别为34%~75%和42%~57%。     

多视图协同的海洋多要素环境数据关联关系分析方法

海洋事件离不开各要素环境数据的共同作用,获取要素之间的关联关系从而进行海洋事件的预报预测,是一个亟待解决的问题。为此,本文提出一种多视图协同的关联关系分析方法来度量海洋各要素数据间的关联关系。首先,在传统平行坐标技术的基础上增加刷技术、轴排序等功能对海洋多要素数据进行初步探索,同时引入散点矩阵图展示各要素的分布;其次,以平行坐标中数据线间的角度、面积以及散点图中要素分布的距离为差异度量方式,对计算得到的差异构建相似性矩阵;再次,采用多维标度法得到原始多要素数据在低维空间中的表达;最后,使用K-means算法对降维后的低维度数据进行聚类分析。本文提出的方法从视觉角度对数据进行分析和特征挖掘,并得到高维数据在低维空间上的可视化展示,实现了有效量化海洋数据不同要素间的相关关系。     

PSO-BP网络算法在运动要素解算中的应用

为了改善被测目标运动要素计算精度,提出了采用 PSO-BP 神经网络算法作为运动要素解算的方程。 该算法将粒子群算法作为 BP 神经网络的学习算法,提高 BP 网络的全局收敛性和收敛速度,将观测到的运动目标参数作为 PSO-BP 神经网络的输入,并将运动目标的方位作为主要输出量,将运动目标的方位值与误差期望值进行比较并作为 PSO 的输入修改 BP 网络权值,进而得到高精度 BP 神经网络。 对该算法进行仿真计算,结果表明:基于该算法的运动目标运动要素解算,尤其是运动方位的解算器精度可以达到 0. 128°,提高了运动要素解算的精度和速度。     

Studies on diffusion and profiles of elements in deep-sea manganese nodules

Elemental compositions are measured in manganese nodules collected from the Northern Mid-Pacific floor by inductively-coupled plasma atomic emission spectrometry (1CP-AES) and their growth rates are determined by radiometric methods. The result shows that depth distributions of elements in nodules vary with depth as follows; (i) increase, (ii) decrease and (iii) fluctuation. These internodule variations in elemental compositions are considered to be caused by diffusion and migration of elements in nodules and heterogeneities in textures of nodules. In the present paper, a diffusive model is used to elucidate the inward-increase profile of some elements in nodules. The effective diffusive coefficients are estimated to be of the order of 10-9 cm2/a for Ni, V and Zn in the nodules, which is less than the value reported for radionuclides.     

海洋信息组织与存储模型研究及其在"数字海洋"中的应用

基于中国数字海洋建设的经验和成果,制定了海洋数据要素的分类方案,将海洋信息分为5大类:海洋点要素、海洋线要素、海洋面要素、海洋网格要素、海洋动态要素.采用基于特征的方法和面向对象的技术设计了适合数字海洋大型信息系统工程建设的时空数据模型,探讨了海洋空间数据模型、海洋立体格网数据模型、关系数据模型在数字海洋数据仓库建设中...     

用X射线分析显微镜对海藻元素的研究Ⅱ.裙带菜孢子叶的元素定位

X射线分析显微镜是一种快速的非破坏分析方法,可以用来对海藻中特定的元素在组织水平进行定位。本实验采用X射线分析显微镜对1997年2月在日本佐贺县唐津市海岸采集的养殖裙带菜(Undaria pinnatifida Suringar)的孢子叶进行了硫、钾、钙、碘的组织定位研究,对孢子叶的整体进行X射线扫描及特征元素次级荧光的图像分析,并选取孢子叶的边缘部、中部及中心各一点进行定点的X射线荧光光谱测定。Ⅹ射线荧光光谱的结果表明,钾是裙带菜孢子叶的最显著元素,具有最大的X射线荧光强度。定位分析表明,钾在孢子叶的中心部位分布较高,钙与碘则在边缘部分布较高,硫多位于孢子叶的中间部分,在中心部位及边缘部的分布均较低。除了钾、钙、硫以外,其他元素如铁、溴、锌也能够在X射线荧光光谱中给出谱峰。作者得到的X射线特征元素荧光图像首次报道了裙带菜孢子叶中钾、钙、硫等元素在组织水平的定位。应用RGB图像彩色合成技术获得的硫、钙、钾三元素的彩色合成图像也与定点分析结果相一致。     

中太平洋北部锰结核的主要元素化学

本文测定了中太平洋北部锰结核的主要化学元素的含量。研究表明,元素的含量分布与组成锰结核的主要矿物有关;与共生元素及渗入锰结核中的粘土矿物和其他碎屑矿物有关。文中还指出了锰结核中富Mn贫Ca,沉积物中富Ca贫Ti,而沉积物对Ca的富集又与海洋生物相关。同时说明,Mg在锰结核与沉积物之间的交换比例约为1∶1。锰结核区的海水深度、pH和Eh值的大小对锰结核的形成产生重要影响。     

等离子质谱(ICP-MS)对高含量元素硫样品中的微量元素分析前处理方法初探

用等离子质谱(ICP-MS)分析一些特殊样品的时候,前处理方法成为分析样品成功与否的关键,对于高基质含量的样品测量其微量元素含量更是如此。元素硫超过99%的自然硫样品中微量元素的测定一般使用燃烧的方法去除自然硫,但是一些易挥发性的元素也因此失去而测不出来。作者试图采用硫升华的方法去除硫基质,通过在原样品中加入内标,分析测定后计算内标的回收率确定出元素Be,Sn,Sc,U和稀土元素(REE)的回收率都在90%以上,可以用升华硫方法很好地测定,而元素Tl,Hf,W,Nb,Zr,Ta等的回收率则在75%以下,不适合用该种方法测定。