Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface

Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA(+)) or ClO4- is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k(12), is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K4Fe(CN)(6) in water when the concentration of TCNQ in the DCE phase is in excess. The k(12) dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ and ferricyanide, k(21), is also obtained by SECM and these results cannot be explained by the same manner.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

EFFECT OF ETHYLENE-PROPYLENE COPOLYMER WITH RESIDUAL PE CRYSTALLINITY ON MECHANICAL-PROPERTIES AND MORPHOLOGY OF PP/HDPE BLENDS

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispersed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. (C) 1995 John Wiley & Sons, Inc.

VISCOSITY AND FLOW PROPERTIES OF CONCENTRATED-SOLUTIONS OF CHITOSAN WITH DIFFERENT DEGREES OF DEACETYLATION

The effects of the degree of deacetylation (DD) on the viscosity and flow behaviour of concentrated solutions of chitosan were investigated using 0.2 M CH3COOH and 0.2 M CH3COOH/0.1 M CH3COONa aqueous solutions as solvents. The results indicated that the

THE VISCOSITY BEHAVIOUR OF SEP BLOCK COPOLYMER SOLUTION DURING ITS MICELLIZATION

The viscosities of polystyrene-b-poly (ethylene/propylene) diblock copolymer in mixed solvent of n-octane and benzene were measured. The influences of the constitution of the mixed solvent, temperature and concentration were on the viscosity investigated. During the micellization the solution viscosity increases rapidly. The results are consistent with the study on the micellization by light scattering. The average mass of micelleswas measured and the hydrodynamic radius of gyrations were calculated.

THE COMPOSITIONS AND STRUCTURES OF SOME COMPOUNDS IN THE SYSTEM CA-SR-CU-O

The system of Ca-Sr-Cu-O have been investigated. Two new compounds with compositions Sr3Cu5O8+alpha and CaSrCu3O5+alpha have been discovered. Both are orthorhombic with a = 6.489, b = 11.280, c = 12.240 angstrom for CaSrCu3O5+alpha and a = 3.950, b = 11.479, c = 13.420 angstrom for Sr3Cu5O8+alpha. The X-ray powder data for CaSrCu3O5+alpha, Sr3Cu5O8+alpha, Sr2CuO3 and SrCuO2 are presented. The oxidation state of Cu ion and oxygen contents are analyzed by iodometric titration. Sr0.5Ca0.5CuO2 that has a similar structure with SrCuO2 has been found and its X-ray data are presented also.

Helium, neon and argon isotope compositions of fluid inclusions in massive sulfides from the Jade hydrothermal field, the Oldnawa Trough

Helium, neon and argon isotope compositions of fluid inclusions have been measured in massive sulfide samples from the Jade hydrothermal field in the central Okinawa Trough. Fluid-inclusion He-3/He-4 ratios are between 6.2 and 10.1 times the air value (Ra), and with a mean of 7.8Ra, which are consistent with the mid-ocean ridge basalt values [He-3/He-4 approximate to (6Rasimilar to 11Ra)]. Values for Ne-20/Ne-22 are from 10.7 to 11.3, which are significantly higher than the atmospheric ratio (9.8). And the fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 334, which are close to the atmosperic values (295.5). These results indicate that the noble gases of trapped hydrothermal fluids in massive sulfides are a mixture of mantle- and seawater-derived components, and the helium of fluid inclusions is mainly from mantle, the nelium and argon isotope compositions are mainly from seawater.

He, Ne and Ar isotope compositions of fluid inclusions in hydrothermal sulfides from the TAG hydrothermal field, Mid-Atlantic Ridge

Helium, rieon and argon isotope compositions of fluid inclusions have been measured in hydrothermal sulfide samples from the TAG hydrothermal field at the Mid-Atlantic Ridge. Fluid-inclusion He-3/He-4 ratios are 2.2-13.3 times the air value (Ra), and with a mean of 7.2 Ra. Comparison with the local vent fluids (He-3/He-4=7.5-8.2 Ra) and mid-ocean ridge basalt values (He-3/He-4=6-11 Ra) shows that the variation range of He-3/He-4 ratios from sulfide-hosted fluid inclusions is significantly large. Values for Ne-20/Ne-22 are from 10.2 to 11.4, which are significantly higher than the atmospheric ratio (9.8). And fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 359, which are close to the atmospheric values (295.5). These results indicate that the noble gases of fluid inclusions in hydrothermal sulfides are a mixture of mantle- and seawater-derived noble gases; the partial mantle-derived components of trapped hydrothermal fluids may be from the lower mantle; the helium of fluid inclusions is mainly from upper mantle; and the Ne and Ar components are mainly from seawater.

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze river) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0-2 cm) were 5-10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C-26-C-33 long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC(15) to nC(22) compounds. Long-chain (> C-20) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (< C-20) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk delta(CTOCTOC)-C-13. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.

Biochemical compositions of two dominant bloom- forming species isolated from the Yangtze River Estuary in response to different nutrient conditions

Variations of cellular total lipid, total carbohydrate and total protein content of two dominant bloom-forming species (Skeletonema costatum and Prorocentrum donghaiense) isolated from the Yangtze River Estuary were examined under six different nutrient conditions in batch cultures. Daily samples were collected to estimate the cell growth, nutrient concentration and three biochemical compositions content during 7 days for S. costatum and the same sampling procedure was done every other day during 10 days for P. donghaiense. Results showed that for S. costatum, cellular total lipid content increased under phosphorus (P) limitation, but not for nitrogen (N) limitation; cellular carbohydrate were accumulated under both N and P limitation: cellular total protein content of low nutrient concentration treatments were significantly lower than that of high nutrient concentration treatments. For P. donghaiense, both cellular total lipid content and total carbohydrate content were greatly elevated as a result of N and P exhaustion, but cellular total protein content had no significant changes under nutrient limitation. In addition, the capability of accumulation of three biochemical constituents of P. donghaiense was much stronger than that of S. costatum. Pearson correlation showed that for both species, the biochemical composition of three constituents (lipid, carbohydrate and protein) had no significant relationship with extracellular N concentration, but had positive correlation with extracellular and intracellular P concentration. The capability of two species to accumulate cellular total lipid and carbohydrate under nutrient limitation may help them accommodate the fluctuating nutrient condition of the Yangtze River Estuary. The different responses of two species of cellular biochemical compositions content under different nutrient conditions may provide some evidence to explain the temporal characteristic of blooms Caused by two species in the Yangtze River Estuary. (C) 2008 Elsevier B.V. All rights reserved.

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four US estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (delta(13)C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble "uncharacterized" organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, delta(13) C and stable nitrogen (delta(15)N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples. a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of delta(13)C and delta(15)N measured for bulk HMW-DOM varied from -22.1 to -30.1parts per thousand and 2.8 to 8.9parts per thousand, respectively and varied among the four estuaries studied as well. Among the Compound classes, TCHO was more enriched in C-13 (delta(13)C = -18.5 to -22.8parts per thousand) compared with THAA (delta(13)C = -20.0 to -29.6parts per thousand) and total lipid (delta(13)C = -25.7 to -30.7parts per thousand). The acid-insoluble organic fractions, in general, had depleted C-13 values (delta(13)C = -23.0 to -34.4parts per thousand). Our results indicate that the observed differences in both delta(13)C and delta(15)N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures. Copyright (C) 2004 Elsevier Ltd.

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (delta(13)C) compositions and n-alkane (nC(16-38)) concentrations were measured for Spartina alterniflora, a C-4 marsh grass, Typha latifolia, a C-3 marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. delta(13)C values of organic matter preserved in the upper fresh water site sediment were more negative (-23.0+/-0.3) as affected by the C-3 plants than the values of organic matter preserved in the sediments of middle (-18.9+/-0.8) and mud flat sites (-19.4+/-0.1) as influenced mainly by the C4 marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC(21) to nC(33) long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC(29) was the most abundant homologue in all samples measured. Both delta(13)C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters. (C) 2003 Elsevier Ltd. All rights reserved.

Nutrient compositions of cultured Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay in China

Carbon, nitrogen, phosphorus, silicon composition of cultured two different sized phytoplankton common species of Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay were measured. Carbon, nitrogen, phosphorus, silicon contents in cell were. obvious higher in T. rotula than in S. costatum, but the percents of nitrogen, phosphorus, silicon contents in cell dry mass in T. rotula were lower than those in S. costatum. The dry mass concentrations of nitrogen,phosphorus,silicon in S. costatum were much higher than those in T. rotula, particularly silicon, the former was 6.4 times of the latter, showing that S. costatum could more assimilate these elements. Especially, S. costatum had competitive dominance for assimilating silicon, which is beneficial to its becoming a major dominant species in relative short silicon of the Jiaozhou Bay. There were some differences in numerical value of nutrient ratios both laboratory-cultured phytoplankton and different sized suspended particulates (mainly phytoplankton) in the Jiaozhou Bay, which was caused by the changes of environment. High contents of carbon, nitrogon and relative low phosporus,silicon, high molar ratio of nitrogen to phosphorus (far higher than Redfield value) and low ratio of silicon to phosphorus and silicon to nitrogen (far lower than Redfield values) in the two diatoms and different sized suspended particulates were consistent with those in the seawater. Relative short silicon in the seawater and phytoplankton showed that silicon was possibly affectting phytoplankton growth in the Jiaozhou Bay.

乍得西南部中新生代火山作用与盆地演化

Located in the Central and West African, Chad, which is not well geological explored, is characterized by Mesozoic- Cenozoic intra-continental rift basins. The boreholes exposed that, during Mesozoic-Cenozoic times, volcanic activities were intense in these basins, but study on volcanic rocks is very weak, especially on those embedded in rift basins, and so far systematic and detailed work has still no carried out. Based on the project of China National Oil and Gas Exploration and Development Corporation, “The analysis of reservoir condition and the evaluation of exploration targets of seven basins in block H in Chad”, and the cooperative project between Institute of Geology and Geophysics, CAS and CNPC International (Chad) Co. Ltd., “Chronology and geochemistry studies on Mesozoic-Cenozoic volcanic rocks from southwestern Chad Basins”, systematic geochronology, geochemistry and Sr-Nd-Pb isotopic geochemistry studies on volcanic rocks from southwestern Chad basins have been done in the thesis for the first time. Detailed geochronological study using whole-rock K-Ar and Ar-Ar methods shows the mainly eruption ages of these volcanic rocks are Late Cretaceous- Paleogene. Volcanic rocks in the well Nere-1 and Figuier-1 from Doba basin are products of the Late Cretaceous which majority of the K-Ar (Ar-Ar) ages fall in the interval 95-75 Ma, whereas volcanic rocks in the well Ronier-1 from Bongor Basin and the Well Acacia-1 from Lake Chad Basin formed in the Paleogene which the ages concentrated in 66-52Ma. Two main periods of volcanic activity can be recognized in the study area, namely, the Late Cretaceous period and the Paleogene period. Volcanic activities have a general trend of south to north migration, but this may be only a local expression, and farther future studies should be carried on. Petrology study exhibits these volcanic rocks from southwestern Chad basins are mainly tholeiitic basalt. Major- and trace elements as well as Sr-Nd-Pb isotopic geochemistry studies show that the late Cretaceous and the Paleogene basalts have a definitely genetic relationship, and magmas which the basalts in southwestern Chad basins derived from were produced by fractional crystallization of olivine and clinopyroxene and had not do suffered from crustal contamination. These basalts are prominently enriched light rare earth elements (LREE), large-ion lithophile elements (LILE) and high field strength elements (HFSE) and depleted compatible elements. They have positive Ba, Pb, Sr, Nb, Ta, Zr, Hf anomalies and negative Th, U, P,Y anomalies. It is possible that the basalts from southwestern Chad basins mainly formed by mixing of depleted mantle (DM) and enriched mantle (EMⅡ) sources. The late Cretaceous basalts have higher (87Sr/86Sr)i ratios than the Paleogene basalts’, whereas have lower (143Nd/144Nd)i ratios than the latter, showing a significant temporal evolution. The mantle sources of the Late Cretaceous basalts may have more enriched mantle(EMⅡ) compositions, whereas those of the Paleogene basalts are relatively more asthenospheric mantle (DM) components. The mantle components with temporal change observed in basalts from Chad basins were probably correlated with the asthenospheric mantle upwelling and lithospheric thinning in Central and Western Africa since Mesozoic. Mesozoic- Cenozoic Volcanism in Chad basins probably is a product of intra- plate extensional stress regime, corresponded to the tectonic setting of the whole West and Central African during Cretaceous. Volcanism is closely correlated with rifting. As time passed from early period to late, the basaltic magma of Chad basins, characterized with shallower genetic depth, higher density and smaller viscosity, probably indicates the gradual strengthening evolution of the rifting. In the initial rife stage, volcanic activities are absent in the study area. Volcanic activities are basiccally corresponded with the strong extensional period of Chad basins, and the eruption of basalts was slightly lagged behind the extensional period. In the post-rift stage (30-0Ma), these basins shifted to the thermal sag phase, volcanic activities in the study area significantly decreased and then terminated.