Rare earth elements and yttrium in ferromanganese deposits from the South China Sea: distribution, composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements(REE) and yttrium(REY),with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10~(–6) to 2 919.4×10~(–6),with an average value of 1 459.5×10~(–6).Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE(LREE) and heavy REE(HREE) oxides of the ferromanganese deposits in the study area can be classified into four grades: non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.     

Chemistry of marine resources——XVI. A new potassium reagent and its enrichment behaviour for potassium ion in seawater

-This paper first presents a new potassium reagent and efficient enrichment agent for direct recovery of potassium from seawater, i. e. , 1, 2, 4, 5-tetrahydroxybenzen -O, O' , O", O''- tetraacetic acid (TTAH4). The synthetic method of TTAH4, its enrichment behaviour for potassium ion in low concentration solution and seawater, and the chemical structure of its corresponding potassium salt have been investigated. A mechanism which caused the uptake of potassium ion is suggested. Elementary analysis and IR-spectrum determination of the potassium salt proved correct evidence for a polynuclear complex, i. e. , (TTAH3K)n. Thus, the mechanism which caused the uptake of potassium ion may be interpreted in terms of the formation of polynuclear chains as a continual sandwich type coordination complex.     

Characteristics of Scour and Deposition in Front of Breakwaters Under Irregular Broken Clapotis

First the scour and deposition patterns of the sandy seabed in front of a vertical breakwater under the action of irregular broken clapotis are investigated experimentally and classified into five types: scour type Ⅰ , scour type Ⅱ, scour type Ⅲ, deposition type Ⅰ, and deposition type Ⅱ . Secondly, the processes of formation of scour and deposition patterns are probed in comparison with those induced by regular broken clapotis and standing waves. Thirdly, the criteria for distinguishing scour and deposition patterns under irregular broken clapotis are presented.     

Chemistry of marine resources——ⅩⅥ. A new potassium reagent and its enrichment behaviour for potassium ion in seawater

This paper first presents a new potassium reagent and efficient enrichment agent for direct recovery of potassium from seawater,i.e.,1,2,4,5-tetrahydroxybenzen -O,O'',O",O''"-tetraacetic acid (TTAH₄).The synthetic method of TTAH₄,its enrichment behaviour for potassium ion in low concentration solution and seawater,and the chemical structure of its corresponding potassium salt have been investigated.A mechanism which caused the uptake of potassium ion is suggested.Elementary analysis and IR-spectrum determination of the potassium salt proved correct evidence for a polynuclear complex,i.e., (TTAH₃K)_n.Thus,the mechanism which caused the uptake of potassium ion may be interpreted in terms of the formation of polynuclear chains as a continual sandwich type coordination complex.     

AHP RESIN AND ITS URANIUM ADSORPTION MECHANISM

I. INTRODUCTION AHP resin is a new type of adsorbent and has been studied by the units concernedfor several years. There is little report about this work so far. AHP resin was synthesizedin aqueous phase with tetra-ethylene pentamine (TEPA), epichlorohydrin (ECH) andC-reagent as raw materials, and basic zinc carbonate (P_Z_n) and rubber solvent oil (120Gasoline) as pore-forming material. Compared with the technique of the amorphous lumpresin and that of the resin synthesized in oil phase, the new technique of resin synthesizedin aqueous phase manifests many advantages, such as raising the capacity of uranium-adsorption of the resin, simplifying the after-treatment process, reducing the cost, etc. Sea water, in which all kinds of cation and anion exist, is a system of electrolytes,and the concentrations of many ions are higher than the concentration of uranium for     

Low-temperature alteration of oceanic island basalts and their contribution to transition metal circulation of the ocean

The major elements, rare earth elements （REE） and trace elements of four basalt samples from central and western Pacific ferro- manganese crust provinces have been analyzed using chemical methods and ICP - MS, respectively. The results indicate that the samples have been extensively altered and that the contents of their major elements have changed significantly. However, the similarity of REE partition patterns and trace element contents of basalt samples to those of fresh oceanic island basalts （OIB） indicate that the basalt samples originated as OIB. Because of low-temperature alteration, the contents of A1203 , Fe203 , MnO, K20 and P205 increased, while MgO and FeO decreased. Active components, such as magnesium and iron, were leached from OIB resulting in the relative enrichment of SiO2. The leaching of active components can cause the relative enrichment of REE, while the precipitation of LREE-rich ferromanganese oxides in vesicles and fissures not only causes an increase of REE contents, but also induces ＂fractionation＂ of LREE and HREE. Based on the enrichment mechanism of REE contents, the theoretical quantities of precipitated ferromanganese oxides and the depleted quantities of active components are calculated ： the depleted quantities of active components for the unit mass of fresh basalts vary in the range of 0.15 ～ 0. 657, and the precipitated quantities of ferromanganese oxides for the unit mass of fresh basahs vary in the range of 0. 006 ～ 0. 042. Of the major elements, the two most depleted are iron, and magnesium, with 18.28% ～ 70.95% of iron and 44.50% ～ 93.94% of magnesium in the fresh basalts was leached out. Theoretical calculation and geochemistry results both indicate that low-temperature alteration of basalts can supply abundant amount of metals to seawater, and may play an important role in ocean metal circulation.     

Observations and Estimations of Directional Spectrum of Sea Waves

The directional spectrum is one of the basic characteristics of sea waves. The observations of directional spectrum of sea waves were successfully conducted at platform Bohai 8 during 1991 and 1992 using a wave gage array for the first time in China. Based on the field data, the directional spectrum which depends on the wave growth is given in this paper. Before observations, the effects of the type of gage array, the distance between the gages and the platform itself on the measured results and the precision of some methods for estimating the directional spectrum were investigated and compared with the methods of numerical simulations and model tests of multi-direcitonal irregular waves. This ensures the quality of the observations and estimations of the directional spectrum.     

An in-situ analysis and measurement of thorium-234, uranium isotopes in seawater

A low-level β counting-α spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium-228 simultaneously and an easy operating procedure for the enrichment, radiochemical separating, sampling and measurement of thorium-234 and uranium-238 in the ocean are developed based on the requirements of analyzing export productivity in the euphotic zone via thorium-234-uranium-238 radioactivity disequilibrium. The detecting efficiency both of β and α radiation is higher than 20%. The background of β radiation is less than 0.5 min-1, and the energy resolution of α detector is better than 1%. Total recycle ratio of thorium-234 is about 75%. Using the above apparatus and procedure, the radioactivities of dissolved thorium-234 and uranium-238, particle thorium-234 and uranium-238 in seawater of the South China Sea, the Southern Ocean and the Arctic Ocean were analyzed.     

An Improved Approach for Interaction of Wave with Floating Spheres and Its Applications

To develop and utilize marine resources in the deep sea, the higher requirements for floating structures, which are operated in marine environment for a long term, have been put forward. Reasonable structure type and accurate force analysis are favorable guarantees to improve the survival performance and working performance of the floating structures. Floating spheres fastened by mooring cable were widely used in floating structures. In this paper, the wave forces of the floating sphere are effi...     

Experimental Study on Superficial Sliding of a New Type of Offshore Platform

- In order to verify the theoretical design and computation of a new type of platform, laboratory model test of the superficial sliding of the platform is carried out. Test results show that the requirement for the stability of the platform can be satisfied, and the API-82 criterion can be met. It is also suggested that, in order to enhance the stability of the platform, a buried- pad with porous holes and a long apron-board should be adopted in the design of the new type of platform.     

Relationships Between Tidal Prism and Throat Area of Tidal Inlets Along Yellow Sea and Bohai Sea Coasts

The relationship between P (spring tidal prism) and A (throat area below mean sea level) is statistically analysed in terms of 29 tidal inlets or bays along the Huanghai Sea (Yellow Sea) and Bohai Sea coasts. For 15 of these tidal inlets, the best regression equation is A(km2) = 0.845 />(km3)1.20. The analysis shows that C and n are little different from those in the P-A relationship for the inlets of the South China Sea and East China Sea coasts. It is noted that the relationship between P and A is unstable because of the difference in sediment abundance. The study shows that a united P-A relationship can be obtained for the tidal inlets of lagoon type and bay-drowned-valley type, not containing some half-circle shape bays which confront deep water. These half-circle bays do not belong to tidal inlets because they do not have enough sediment abundance and are fairly open.     

An Approach to Stability Analysis of Embedded Large-Diameter Cylinder Quay

The large-diameter cylinder structure, which is made of large successive bottomless cylinders placed on foundation bed or partly driven into soil, is a recently developed retaining structure in China. It can be used in port, coastal and off-shore works. The method for stability analysis of the large-diameter cylinder structure, especially for stability analysis of the embedded large-diameter cylinder structure, is an important issue. In this paper, an idea is presented that is, em-bedded large-diameter cylinder quays can be divided into two types, i.e. the gravity wall type and the cylinder pile wall type. A method for stability analysis of the large-diameter cylinder quay of the cylinder pile wall type is developed and a method for stability analysis of the large-diameter cylinder quay of the gravity wall type is also proposed. The effect of sig-nificant parameters on the stability of the large-diameter cylinder quay of the cylinder pile wall type is investigated through numerical calculation.     

Bioaccumulation of polychlorinated biphenyls in prawns and a mud crab from mixed-aquaculture ponds

The bioaccumulation of ten polychlorinated biphenyl (PCB) congeners was investigated within different tissues in three prawns (Penaeusorientalis Kishinouce, Laomedia astacina de Haan and Penaeus vannamei Boone) and one mud crab (Scylla serrata Forsskal) from mixed-aquaculture ponds in Taizhou in April 2007. The average concentrations (wet mass) of Σ PCBs in muscle, head, and rind tissues for mean among these prawn species were 7.04, 21.16, and 11.47 ng/g, respectively. The average concentrations of Σ PCBs in muscle, branchia, and spawn in Scylla serrata were 6.49, 21.13, and 19.76 ng/g, respectively. The concentrations of CB28 were the highest in prawn tissues (2.40 ng/g), and accounted for 18.60% of Σ PCBs. The concentration of CB52 was the lowest. The application of principal component analysis (PCA) for the estimation of PCB sources of contamination resulted in first component main contributions of CB101, CB153 and CB28 in the muscle, head, and rind in combined prawn samples, respectively. The enrichment level of Σ PCBs for different tissues varied greatly. The accumulation coefficient of Σ PCBs in prawn muscle, head, and rind tissues were 396.35, 1 191.79, and 645.91, respectively. For the Scylla serrata, the accumulation coefficients were 365.81, 1 190.50, and 1 113.31 for muscle, branchia, and spawn tissues, respectively. For prawns, the accumulation coefficient of CB153 was the highest in muscle tissues, while CB155 had the highest coefficients in the head and rind tissues. The CB155 coefficient was the highest in spawn tissues of the mud crab.     

Preliminary study on the distribution of nutrients, organic matter, trace metals in sea surface microlayer in Xiamen Bay and Jiulong Estuary

-The enrichment of nutrients (NOa-, NOa-, PO43-), suspended particles, organic matter (POC, PON,DOC) , and trace metals (Cu, Ni, Cd) was determined in the sea surface microlayer of Xiamen Bay and Jiulong Estuary. The mean enrichment factors ([Xi]microlayer/[Xi ]15cm in depth) mostly ranged between 1 . 0 and 2. 0. The dissolved forms were the major forms of the components measured, the enrichment of dissolved organic matter and suspended particles could lead to the changes in the total amount and speciation of nutrients and trace metals. No correlation was observed between sample concentrations, speciation, enrichment factors and sample locations. However, some evidence shows that these parameters are correlated with sea state, indicating the complexity and dynamic nature of the sea surface microlayer.     

Non-Simultaneous Failure of Ice in Front of Multi-Leg Structures

Because the multi-leg jacket structure is the major type of offshore structures in the Bohai Sea, the study of non-si-multaneous failure of i鏴 on multi-leg structures is important. However, the non-simultaneous failure has not been consid-ered in engineering design until now, obviously resulting in costly design and notable waste. To resolve this problem, this paper, by means of analysis of experimental data, calculates the coefficient of the non-simultaneous failure for the double-pile structure, the square four-leg structure, the single-line multi-pile structure, and the conical structure, respectively, and provides some reference criteria for engineering design.     

Investigation on the Performance of Articulated Buoys

Articulated buoys become more and more popular by the marine management departments as a new type of aids to navigation, for they possess an excellent hydrodynamic performance with small static heel angle in wind and current and small rolling in wave and accurate position. The structure of articulated buoys and calculation method of their hydrodynamic performance are introduced in this paper. A scries of experiments has been conducted in the State Key Laboratory of Ocean Engineering of China and useful results achieved for providing a design optimization basis.     

Numerical Analysis of Interaction Between Pile-Supported Pier and Bank Slope

Two- and three-dimensional finite element analysis programs for pile-soil interaction are compiled. Duncan-Chang's Model is used. The construction sequence of the pier is modeled. The pile-soil interface element is used. The influence of the combination type of piles on the deformation of bank slope and pile behaviour is analyzed. Different designs of a pile-supported pier are compared thoroughly. Calculation results show that the stresses and displacements of the pile are directly related to the distance from the bank slope and the direction of inclination. An inclined prop pile set in the rear platform would remarkably reduce the stresses of piles and the displacement of the pier.     

Seasonal variations of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer and subsurface water of Jiaozhou Bay and its adjacent area

The distributions of DMS and its precursor dimethylsulfoniopropionate, in both dissolved (DMSP_d) and particulate fractions (DMSP_p) were determined in the seasurface microlayer and corresponding subsurface water of the Jiaozhou Bay, China and its adjacent area in May and August 2006. The concentrations of all these components showed a clear seasonal variation, with higher concentrations occurring in summer. This can be mainly attributed to the higher phytoplankton biomass observed in summer. Simultaneously, the enrichment extents of DMSP_d and DMSP_p in the microlayer also exhibited seasonal changes, with higher values in spring and lower ones in summer. Higher water temperature and stronger radiant intensity in summer can enhance their solubility and photochemical reaction in the microlayer water, reducing their enrichment factors (the ratio of concentration in the microlayer to that in the corresponding subsurface water). A statistically significant relationship was found between the microlayer and subsurface water concentrations of DMS, DMSP and chlorophyll a, demonstrating that the biogenic materials in the microlayer come primarily from the underlying water. Moreover, our data show that the concentrations of DMSP_p and DMS were significantly correlated with the levels of chlorophyll a, indicating that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. The ratios of DMS/chlorophyll a and DMSP_p/chlorophyll a varied little from spring to summer, suggesting that there was no obvious change in the proportion of DMSP producers in the phytoplankton community. The mean sea-to-air flux of DMS from the study area was estimated to be 5.70 μmol/(m²·d), which highlights the effects of human impacts on DMS emission.     

The Study of Fish Eggs, Larvae and Juveniles of the Estuary at Beitang

The fish eggs, larvae and juveniles were collected during 25 cruises from April to No-vember 1980 and 1981 respectively. They were represented by 40 species, 36 genera, 19families and 9 orders. According to their habit, the fish eggs, larvae and juveniles couldbe referred to three types: (1) shallow sea and estuary type; (2) migration type of outersea; (3) fresh water type. The shallow sea and estuary species were 29 in number, occu-pying 72.5% of the total; the migration species were 3 in number, occupying 7.5% of thetotal; the fresh water species were 8 in number occupying 20% of the total.     

Elemental geochemical records of seafloor hydrothermal activities in the sediments from the Okinawa Trough

The major and minor element contents in the sediment core H9 from the hydrothermal fields of the Okinawa Trough show a sharp change at the depth of 80 cm. The elements enriched in the upper 80 cm core are those enriched in the hydrothermal deposits and in the surface sediments recovered from the hydrothermal fields in the trough, which indicates the input of hydrothermal materials. Comparing with other hydrothermal sediments from Mid-ocean Ridges or the Lau Basin, the degree of the enrichment of elements iron, copper,cobalt, and nickel is relatively low. However, the enrichment of elements manganese, lead, arsenic, antimony and mercury is remarkable. The average contents of these elements in the upper 80 cm core sediments are three to six times those in the lower section, and 3~12 times those in the surface sediments which are not influenced by hydrothermal activities. Hydrothermal activities have contributed significant manganese, lead, arsenic, antimony and mercury to the sediments, and these elements are distinct indicators for the hydrothermal activity in the Okinawa Trough. The significant enrichment of these elements in Core H9 upward from the depth 80 cm indicates the start or the significant enhancing of the hydrothermal activity in this area at about 5 740 aB.P. The average accumulation rate of manganese during this period is about 40 461 μg/(cm2·ka), which is similar to the hydrothermal sediments in the Lau Basin or the East Pacific Rise.