Trends in heavy metal levels in the dissolved and particulate phase in the Dutch rhine-meuse (MAAS) delta*

Levels of the heavy metals Cd, Cr, Cu, Pb and Zn, in both the dissolved and particulate phase, were determined in two sampling campaigns in August 1978 and August 1984 in the Dutch Rhine-Meuse (Maas) Delta. Besides the heavy metal concentrations, other important parameters were determined, such as the concentrations of seston, chlorophyll and nutrients. The concentrations of dissolved Cd and of Cd, Pb and Cu in particulate matter were much higher in 1978 than in 1984, especially for Cd. This may be due to the strict regulations implemented in Germany to reduce the pollution of natural waters by heavy metals. The correlation between the high Cd content and the chlorophyll content is explained by the binding of Cd to living and dead organisms. The distribution of the metals between the dissolved and the particulate phase, indicated by the distribution quotient Kd , increases from low values of Kd for Cu and Zn, to higher values for Cd and Cr, and the highest values for Pb. The differences are explained by various binding forms of each of these metals in natural waters

Synthesis and characterization of Prussian blue@platinum nanoparticle hybrids from a mixture solution of platinum nanocatalyst and ferric ferricyanide

In the present study, platinum nanoparticles modified with Prussian blue (PB) have been synthesized by a heterogeneous catalytic reaction. Transmission electronic microscopy (TEM) confirmed the deposition of nanoclusters around the Surfaces of platinum particles, and spectroscopic studies verified that the molecular composition of the nanoclusters was dominantly PB and a minority of platinum ferricyanide. Thus, it was shown that the platinum particles behaved not only as catalysts for the growth of PB, but also as a reactant to generate a PB analogue complex.

Synthesis and characterization of new carbazole/fluorene-based derivatives for blue-light-emitting devices

2,7-Bis(9-ethylcarbazol-3-yl)-9,9-di(2-ethylhexyl)fluorene and a segmented copolymer composed of the same chromophores alternated with hexamethylene fragments were synthesized. The obtained materials possess good solubility in common organic solvents, high thermal stability with 1% weight loss temperature of 350-370 degrees C, and suitable glass transition temperatures. Both derivatives show blue fluorescence in dilute solutions as well as in solid state, demonstrating that excimers are not formed in the thin films. The fluorescence spectra of the materials do not show any peaks in the long-wavelength region even after annealing at 200 degrees C in air. An organic LED with the configuration of ITO/copolymer/Al generates blue electroluminescence with the maximum peak at 416 nm, rather low turn-on voltage (4.0 V), and brightness of about 400 cd/m(2). The heterostructure device based on model derivative emitted stable blue light with low operation voltage (100 cd/m(2) at similar to 11 V) and demonstrated luminescence efficiency of 0.8 cd/A.

Crystallization and phase behavior of crystalline syndiotactic 1,2-polybutadiene/isotactic polypropylene blends in solution-cast thin films

Crystallization and phase behavior in solution-cast thin films of crystalline syndiotactic 1,2-polybutadiene (s-1,2-PB) and isotactic polypropylene (i-PP) blends have been investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM) techniques. Thin films of pure s-1,2-PB consist of parallel lamellae with the c-axis perpendicular to the film plane and the lateral scale in micrometer size, while those of i-PP are composed of cross-hatched and single-crystal-like lamellae. For the blends, TEM and AFM observations show that with addition of i-PP, the s-1,2-PB long lamellae become bended and i-PP itself tends to form dispersed convex regions oil a continuous s-1,2-PB phase even when i-PP is the predominant component, which indicates a strong phase separation between the two polymers during film formation. FESEM micrographs of both lower and upper surfaces of the films reveal that the s-1,2-PB lamellae pass through i-PPconvex regions from the bottom, i.e. the dispersed i-PP regions lie on the continuous s-1,2-PB phase. The structural development is attributed to an interplay of crystallization and phase separation of the blends in the film forming process.

Polymer concentration, shear and stretch field effects on the surface morphology evolution during the spin-coating

Polymer concentration and shear and stretch field effects on the surface morphology evolution of three different kinds of polymers (polystyrene (PS), polybutadiene (PB) and polystyrene-b-polybutadiene-b-polystyrene (SBS)) during the spin-coating were investigated by means of atomic force microscopy (AFM). For PS and SBS, continuous film, net-like structure and particle structure were observed at different concentrations. For PB, net-like structures were not observed and continuous films and radial array of droplets emerged. Moreover, we compared surface morphology transitions on different substrate locations from the center to the edge. For PS, net-like structure, broken net-like structure and irregular array of particles were observed. For SBS, net-like structure, periodically orientated string-like structure and broken-line structure appeared. But for PB, flower-like holes in the continuous film, distorted stream-like structure and irregular distributions of droplets emerged. These different transitions of surface morphologies were discussed in terms of individual material property.

Cyclic voltammetric and in situ Fourier transform infrared spectroelectrochemical studies on the reaction of Cd2+ on the plussian blue/platinum modified electrode

Plussian blue(PB)/Pt modified electrode Tvas studied in the CdCl2 electrolyte solution by cyclic voltammetry and in situ FTIR spectroelectrochemistry. It was found that Cadmium ion was capable of substituting the high-spin iron of PB in an electrochemically induced substitution reaction and hexacyanoferrate cadmium (CdHCF) can be formed in the PB film. But PB and CdHCF in mixture film showed their own electrochemistry properties without serious effect on each other. The mechanism of substitution reaction has been given in detail.

Allelopathic interactions between the macroalga Ulva pertusa and eight microalgal species

HETEROSIGMA-AKASHIWO RAPHIDOPHYCEAE; CENTRAL VENICE LAGOON; ALEXANDRIUM-TAMARENSE; RED-TIDE; COASTAL LAGOONS; PHYTOPLANKTON; GROWTH; BAY; DINOFLAGELLATE; COMPETITION

Ulva and Enteromorpha (Ulvaceae, Chlorophyta) from two sides of the Yellow Sea: analysis of nuclear rDNA ITS and plastid rbcL sequence data

Ulvacean green seaweeds are common worldwide; they formed massive green tides in the Yellow Sea in recent years, which caused marine ecological problems as well as a social issue. We investigated two major genera of the Ulvaceae, Ulva and Enteromorpha, and collected the plastid rbcL and nuclear ITS sequences of specimens of the genera in two sides of the Yellow Sea and analyzed them. Phylogenetic trees of rbcL data show the occurrence of five species of Enteromorpha (E. compressa, E. flexuosa, E. intestinalis, E. linza and E. prolifera) and three species of Ulva (U. pertusa, U. rigida and U. ohnoi). However, we found U. ohnoi, which is known as a subtropical to tropical species, at two sites on Jeju Island, Korea. Four ribotypes in partial sequences of 5.8S rDNA and ITS2 from E. compressa were also found. Ribotype network analysis revealed that the common ribotype, occurring in China, Korea and Europe, is connected with ribotypes from Europe and China/Japan. Although samples of the same species were collected from both sides of the Yellow Sea, intraspecific genetic polymorphism of each species was low among samples collected worldwide.

Modification to the Hardisty equation, regarding the relationship between sediment transport rate and particle size

Bagnold-type bed-load equations are widely used for the determination of sediment transport rate in marine environments. The accuracy of these equations depends upon the definition of the coefficient k(1) in the equations, which is a function of particle size. Hardisty (1983) has attempted to establish the relationship between k(1) and particle size, but there is an error in his analytical result. Our reanalysis of the original flume data results in new formulae for the coefficient. Furthermore, we found that the k(1) values should be derived using u(1) and u(1cr) data; the use of the vertical mean velocity in flumes to replace u(1) will lead to considerably higher k(1) values and overestimation of sediment transport rates.

Geochemical and isotopic characteristics of volcanic rocks from the northern East China Sea shelf margin and the Okinawa Trough

Volcanic rocks both from the northern East China Sea (NECS) shelf margin and the northern Okinawa Trough are subalkaline less aluminous, and lower in High Field Strength Elements (HFSE). These rocks are higher in Large Ion Lithophile Elements (LILE), thorium and uranium contents, positive lead anomalies, negative Nb-Ta anomalies, and enrichment in Light Rare Earth Elements (LREE). Basalts from the NECS shelf margin are akin to Indian Ocean Mid-Ocean Ridge Basalt (MORB), and rhyolites from the northern Okinawa Trough have the highest Pb-207/Pb-208 and Pb-208/Pb-204 ratios. The NECS shelf margin basalts have lower Sr-87/Sr-86 ratios, epsilon(Nd) and sigma O-18 than the northern Okinawa Trough silicic rocks. According to K-40-Ar-40 isotopic ages of basalts from the NECS shelf margin, rifting of the Okinawa Trough may have been active since at least 3.65-3.86 Ma. The origin of the NECS shelf margin basalt can be explained by the interaction of melt derived from Indian Ocean MORB-like mantle with enriched subcontinental lithosphere. The basalts from both sides of the Okinawa Trough may have a similar origin during the initial rifting of the Okinawa Trough, and the formation of basaltic magmas closely relates to the thinning of continental crust. The source of the formation of the northern Okinawa Trough silicic rocks was different from that of the middle Okinawa Trough, which could have been generated by the interaction of basaltic melt with an enriched crustal component. From the Ryukyu island arc to East China, the Cenozoic basalts have apparently increasing trends of MgO contents and ratios of LREE to Heavy Rare Earth Elements (HREE), suggesting that the trace element variabilities of basalts may have been influenced by the subduction of the Philippine Sea plate, and that the effects of subduction of the Philippine Sea plate on the chemical composition of basaltic melts have had a decreasing effect from the Ryukyu island arc to East China.

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH2OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl2 extractable fraction. A large proportion of Cu was bound to the acidic H2O2 extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier's procedure, and the order of mobility was Zn > Cd > Cu > Ce > Pb.

Isolation and identification of bacteria associated with the surfaces of several algal species

We conducted this study to assess the diversity of bacteria associated with the surfaces of algae based on 16S rDNA sequence analyses. Twelve strains of bacteria were obtained from the surfaces of the following four species of algae: Gracilaria textorii, Ulva pertusa, Laminaria japonica, and Polysiphonia urceolata. The isolated strains of bacteria can be divided into two groups: Halomonas and Vibrio, in physiology, biochemical characteristics and 16S rDNA sequence analyses. The phylogenetic tree constructed based on 16S rDNA sequences of the isolates shows four obvious clusters, Halomonas venusta, Vibrio tasmaniensis, Vibrio lentus, and Vibrio splendidus. Isolates from the surface of P. urceolata are more abundant and diverse, of which strains P9 and P28 have a 16S rDNA sequence very similar (97.5%-99.8%) to that of V. splendidus. On the contrary, the isolates from the surfaces of G textorii, U. pertusa and L. japonica are quite simple and distribute on different branches of the phylogenetic tree. In overall, the results of this study indicate that the genetic relationships among the isolates are quite close and display a certain level of host species specificity, and alga-associated bacteria species are algal species specific.

Trace metal concentrations in suspended particles, sediments and clams (Ruditapes philippinarum) from Jiaozhou Bay of China

Suspended particulate matter (SPM), sediments and clams were collected at three sites in Jiaozhou Bay to assess the magnitude of trace metal pollution in the area. Metal concentrations in SPM (Cu: 40.11-203; Zn: 118-447; Pb: 50.1-132; Cd: 0.55-4.39; Cr: 147.6-288; Mn: 762-1670 mu g/g), sediments (Cu: 17.64-34.26; Zn: 80.79-110; Pb: 24.57-49.59; Cd: 0.099-0.324; Cr: 41.6-88.1; Mn: 343-520 mu g/g) and bivalves (Cu: 6.41-19.76; Zn: 35.5-85.5; Pb: 0.31-1.01; Cd: 0.51-0.67; Mn: 27.45-67.6 mu g/g) are comparable to those reported for other moderately polluted world environments. SPM showed a less clear pattern. Metal concentrations in sediments displayed a clear geographical trend with values increasing with proximity to major urban centers. The clams (on dry weight) showed a complex pattern due to the variability introduced by age-related factors. Cd showed an apparent reverse industrial trend with higher concentrations in clams collected at distant stations. Zn, Pb and Mn showed no clear geographical pattern, whereas Cu increased in the clams collected in the most industrialized area. In addition, the bioaccumulation factors (BAF) were calculated. The result indicated that the studied Ruditapes philippinarum in Jiaozhou Bay possessed different bioaccumulation capacities for Cd, Zn, Cu, Pb and Mn, and Cd, Zn had a relatively high assimilation of those metals from sediment particles. A significant relationship with clam age was observed for Zn (positive) and Cu (negative) suggesting different physiological requirements for both metals with age. Trace metal concentrations measured in the tissue of the investigated clam were in the range considered safe by the WHO for human use.

中国东部沙地物源示踪及地质意义

Heavy mineral assemblages, chemical compositions of diagnostic heavy minerals such as garnet and tourmaline, and U-Pb ages and Hf isotopic compositions of zircons are very effective means to determine sediment provenance. An integrated application of the above provides insight on the lithologies, crystallization ages and crustal formation ages of the parent magma of sediment source areas. As a result, the locations and characteristics of potential source areas can be constrained and contributions of different source regions may be evaluated. In addition, the study provides evidence for the magmatic and tectonic history of source areas using a novel approach. The heavy mineral assemblages, and chemical compositions of detrital garnets and tourmalines, U-Pb ages and Hf isotopic compositions of zircons for sand and loess samples deposited since the Last Glacial Maximum (LGM) from the Hulunbeier, Keerqin and Hunshandake sandlands were analyzed and compared to those of central-southern Mongolia, the central Tarim and surrounding potential source areas, the Central Asian Orogenic Belt (CAOB) and North China Craton (NCC). The following remarks on provenance and tectonic history can be made: 1. The source compositional characteristics of the Hulunbeier, Keerqin and Hunshandake sandlands are similar. They are derived from the CAOB and NCC whose contributions for the Keerqin and Hunshandake sandland are about 50%. For the Hulunbeier sandland it is somewhat less, about 40%. 2. Loesses around of the sandlands have the identical source signiture as the sands, implying that they are sorted by the same wind regime. 3. The source characteristics of the present and LGM sands are the same, providing direct evidence that the present sands originated from the reworking of LGM sands. 4. The provenance characteristics of the three sandlands differ from those of the Tarim. As a result, the possibility that the three eastern sandlands were sourced from the Taklimakan desert can be ruled out. 5. The source compositions of sand samples derived from the CAOB indicate that the occurrence of Archean and Paleoproterozoic metamorphic basement rocks is limited and continuous subduction-accretion events from the Neoproterozoic to the Mesozoic occurred. This implies that the CAOB is a orogenic collage belt similar to the present day southwest-Pacific, and formed by the amalgamation of small forearc and backarc ocean basins occurring between island arcs and microcontinents during continuous collision and accretion. The Hf isotopic signitures of detrital zircons indicate that large amounts of juvenile mantle materials were added to the CAOB crust during the Phanerozoic.

塔里木盆地塔中—巴楚地区早二叠世岩浆岩地球化学特征及其成因

Tazhong-Bachu region is located in the Western Tarim basin.The early Permian magmatic rocks occur in the earth surface of Tazhong-Bachu region are mainly distributed in Kepintag,Mazhartag and Wajilitag region. There are a lot of wells, in which researchers found the early Permian magmatic rocks,in desert cover area.Most magmatic rocks are basic rocks, a few of which are ultrabasic rocks and intermediate-acid magmatic rocks.The ultrabasic rocks are are mainly occur in the Cryptoexplosive Breccia Pipes ,which is located in the volcanic complex body of Wajilitag region.The basic rocks can be divided into three rock types：The first type of the magmatic rocks in Tazhong-Bachu region is volcanic rock ,which occurs in the Lower Permian Kupukuziman Formation and Kaipaizileike Formation. Most Volcanic rocks are basalts,a few of which are volcanic breccias and pyroclastic rocks.The basalts are distributed in stratiform occurrences and interbeded the clastic rocks in Kepintag region.The attitudes of the basalts are nearly horizontal.Columnar Joints, gas pore textures and amygdaloidal structure are to develop in basalts.The second type of the magmatic rocks in Tazhong-Bachu region is diabase,which occurs in Mazhartag region.Diabase dike swarms occur in the stratums of Silurian, Devonian, Carboniferous and Lower Permian.They make from NNW direction to SSE direction, the obliquity of stratum is greater than 60°, and the dike thickness is form several cm to several meters. Diabasic texture is found in the rocks .The first type of the magmatic rocks in Tazhong-Bachu region are gabbro- pyroxenite rocks ,which occur in the Wajilitag igneous complex body. The intermediate-acid magmatic rocks, which are mainly syenites, are located in Mazhartag and Wajiltag region. But they are small in the whole Tazhong-Bachu region.There are intermediate-acid magmatic rocks,which are mainly dacite,in the northeast part of the wells in Tazhong-Bachu region.But ,it is not found in earth surface.Through systematical geochemical research of early Permian magmatic rocks,which are distributed in Kepintag,Mazhartag, Wajilitag region and the wells such as F1 well、Z1 well、Z13 well、TZ18 well、H3 well、H4 well et al., the focus on the geochronologic characteristics, the main element,trace element and REE geochemistry, the mineralogic characteristics, the Sr-Nd and Pb isotopic characteristics are put forward. The main points are: 1、A combined study of CL imaging and LA-ICP-MS U-Pb dating were carried out for zircon grains of the magmatic rocks in the Tazhong-Bachu region from the Tarim basin.The results of the systematic zircon LA-ICP-MS U-Pb dating reveal 272±6Ma to 291±10Ma for the magamatic rocks. It indicated that Early Permian is an important period of magmatic acvivity in the Tazhong-Bachu region. 2、There are a big hunch in the curves of primitive mantle-normalized trace element concentrations in the early Permian magmatic rocks from Kepintag, Mazhartag, Wajilitag region and the 14 wells. Light rare earth elements are comparatively rich and heavy rare earth elements are comparatively poor. The slope rates are same between light rare erath elements and heavy rare earth elements. It is not like the curves of the basalts in the convergent margin of plate , in which the slope rates of light rare erath elements is bigger than the alope rates of heavy rare erath elements, and the curves of heavy rare earth elements are comparatively flat. The magmatic rocks of Tazhong-Bachu region rarely have the characteristics of the basalts in the convergent margin of plate, which is that Tantalum, Niobium and Titanium are much poor, and Zirconium, Hafnium and Phosphorus are moderately poor. The magamatic rocks are mostly alkaline, which is indicated by the dots of the (Na2O+K2O)-SiO2 identification diagram. All of these indicate that the early Permian magmatic rocks were formed in an extension environment of intraplate. 3、The Thorium abundance is high and Tantalum abundance is low in most magmatic rocks from Tazhong-Bachu reguion, which is formed for crustal contamination.In the Th/Yb-Ta/Yb identification diagram，most dots are in the region, which means active continental margin, but a few dots are in the region, which means mantle source. It indicated the feeding of continental crust materials. 4、The magnesium content of the olvines from Wagilitag region is richest, and the olvines from Kepintag region is poorest in the tree region. 5、Through the the Sr-Nd and Pb isotopic study of the basalts and diabases from the F1 well core, Z1 well core, Z13 well core,TZ18 well core, and the basalts，gabbros, diabases(diabase-prophyrites) and pl-peridotites from Kepintag,Mazhartag, Wajilitag region , it indicated that all isotopic data is similar and close to enriched mantle.