Selective hydrogenation of nitrobenzene to aniline in dense phase carbon dioxide over Ni/gamma-Al2O3: Significance of molecular interactions

The selective hydrogenation of nitrobenzene (NB) over Ni/gamma-Al2O3 Catalysts Was investigated using different media of dense phase CO2, ethanol, and n-hexane. In dense phase CO2, the total rate of NB hydrogenation was larger than that in organic solvents under similar reaction conditions; the selectivity to the desired product, aniline, was almost 100% over the whole conversion range of 0-100%. The phase behavior of the reactant mixture in/under dense phase CO2 was examined at reaction conditions. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions Of CO2 with the following reactant and reaction intermediates: NB, nitrosobenzene (NSB), and N-phenylhydroxylamine (PHA). Dense phase CO2 strongly interacts with NB, NSB, and PHA, modifying the reactivity of each species and contributing to positive effects on the reaction rate and the selectivity to aniline. A possible reaction pathway for the hydrogenation of NB in/under dense phase CO2 over Ni/gamma-Al2O3 is also proposed.

Formation and evolution of the modern warm current system in the East China Sea and the Yellow Sea since the last deglaciation

To reconstruct the formation and evolution process of the warm current system within the East China Sea (ECS) and the Yellow Sea (YS) since the last deglaciation, the paleoceangraphic records in core DGKS9603, core CSH1 and core YSDP102, which were retrieved from the mainstream of the Kuroshio Current (KC), the edge of the modern Tsushima Warm Current (TWC) and muddy region under cold waters accreted with the Yellow Sea Warm Current (YSWC) respectively, were synthetically analyzed. The results indicate that the formation and evolution of the modern warm current system in the ECS and the YS has been accompanied by the development of the KC and impulse rising of the sea level since the last deglaciation. The influence of the KC on the Okinawa Trough had enhanced since 16 cal kyr BP, and synchronously the modern TWC began to develop with the rising of sea level and finally formed at about 8.5 cal kyr BP. The KC had experienced two weakening process during the Heinrich event 1 and the Younger Drays event from 16 to 8.5 cal kyr BP. The period of 7-6 cal kyr BP was the strongest stage of the KC and the TWC since the last deglaciation. The YSWC has appeared at about 6.4 cal kyr BP. Thus, the warm current system of the ECS and the YS has ultimately formed. The weakness of the KC, indicated by the occurrence of Pulleniatina minimum event (PME) during the period from 5.3 to 2.8 cal kyr BP, caused the main stream of the TWC to shift eastward to the Pacific Ocean around about 3 cal kyr BP. The process resulted in the intruding of continent shelf cold water mass with rich nutrients. Synchronously, the strength of the YSWC was relatively weak and the related cold water body was active at the early-mid stage of its appearance against the PME background, which resulted in the quick formation of muddy deposit system in the southeastern YS. The strength of the warm current system in the ECS and the YS has enhanced evidently, and approached to the modern condition gradually since 3 cal kyr BP.

Spatial variation of suspended particulate matter in the Yellow Sea

A joint oceanographic cruise between the Institute of Oceanography, Chinese Academy of Science and the Department of Oceanography, Seoul National University was carried out in the Yellow Sea during the summer of 1996 to investigate the concentration and particle-size distribution of suspended particulate matter (SPM). The general trends in the surface and bottom waters show that SPM concentrations and particle sizes decreased seawards in both the western (Chinese) and eastern (Korean) coastal regions of the Yellow Sea. In the bottom waters, SPM concentrations were higher and particle sizes were larger along the eastern coast than along the western coast. We suggest this is due to the resuspension of bottom sediments by strong onshore summer typhoons in the southwestern coastal waters of Korea.

Suspended particulate matter fluxes through the Straits of Dover, English Channel: observations and modelling

Suspended Particulate Matter (SPM) concentrations at various levels within the water column, together with salinity and temperature, were measured using water samples collected from six stations across the Straits of Dover. The sampling programme covered a 16-month period, undertaken during 23 cruises. On the basis of the spatial variability in the concentrations, the water bodies are divided by several boundaries, controlled by tidal and wind conditions. Within the water column, SPM concentrations were higher near the sea bed than in the surface waters. Throughout the cross-section, maximum concentrations occurred adjacent to the coastlines. Temporal variability in the SPM concentration exists on daily and seasonal scales within the coastal waters (4.2 to 74.5 mg L-1): resuspension processes, in response to semi-diurnal tidal cycles (with a period of around 12.4 h) and spring-neap cycles (with a period of 15 days) make significant contributions. Distinctive seasonal/annual concentration changes have also been observed. In the offshore waters, such variability is much less significant (0.9 to 6.0 mg L-1). In the summer the English Coastal Zone is associated with relatively high SPM concentrations: the Central Zone has a low and stable SPM concentration between these zones, there is a Transitional Zone, where there is a rapid response of SPM concentration to wind forcing. Finally, the French Coastal Zone is characterized by variable (sometimes high) SPM concentrations. Because of the zonation, SPM fluxes within the Dover Strait are controlled by different transport mechanisms. Within the Central Zone, the flux can be represented by the product of mean water discharges and SPM concentrations. However, within the coastal zones fluctuations in SPM concentrations on various time-scales must be considered. In order to calculate the maximum and minimum SPM fluxes, 10 cells were divided in the strait. A simple modelling calculation has been proposed for this complex area. The effect of spring-neap tidal cycles and seasonal changes can contribute significantly to the overall flux, which is of the order of 20 x 10(6) t.yr(-1) (through the Dover Strait, towards the North Sea). Such an estimate is higher than most obtained previously. (C) 2000 Ifremer/CNRS/IRD/Editions scientifiques et medicales Elsevier SAS.

Resuspension and advection processes affecting suspended particulate matter concentrations in the central English Channel

Suspended particulate matter (SPM) measurements obtained along a cross-section in the central English Channel (Wight-Cotentin transect) indicate that the area may be differentiated into: (1) an English coastal zone, associated with the highest concentrations; (2) a French coastal zone, with intermediate concentrations; and (3) the offshore waters of the Channel, characterised by a very low suspended-sediment load. The SPM particle-size distribution was modal close to the English coast (main mode 10-12 mu m); the remainder of the area was characterised by flat SPM distributions. Examination of the diatom communities in the SPM suggest:; that material resuspended in the intertidal zone and the estuarine environments was advected towards the offshore waters of the English Channel. Considerable variations in SPM concentrations occurred during a tidal cycle: maximum concentrations were sometimes up to 3 times higher than the minimum concentrations, Empirical orthogonal function (EOF) analysis of the SPM concentration time series indicates that, although the bottom waters were more turbid than the surficial waters, this was not likely to be the result of in situ sediment resuspension. Instead, the observed variations appear to be controlled mainly by advective mechanisms. The limited resuspension was probably caused by: (1) the limited availability of fine-grained material within the bottom sediments, and (2) 'bed-armouring' processes which protect the finer-grained fractions of the seabed material from erosion and entrainment within the overlying flow during the less energetic stages of the tide.

Evolution and variation of the Tsushima warm current during the late Quaternary: Evidence from planktonic foraminifera, oxygen and carbon isotopes

The evolution and variation history of the Tsushima warm current during the late Quaternary was reconstructed based on the quantitative census data of planktonic foraminiferal fauna, together with oxygen and carbon isotope records of mixed layer dweller a ruber and thermocline dweller N. dutertrei in piston core CSH1 and core DGKS9603 collected separately from the Tsushima warm current and the Kuroshio dominated area. The result showed that the Tsushima warm current vanished in the lowstand period during 40-24 cal ka BP, while the Kuroshio still flowed across the Okinawa Trough, arousing strong upwelling in the northern Trough. Meanwhile, the influence of freshwater greatly increased in the northern Okinawa Trough, as the broad East China Sea continental shelf emerged. The freshwater reached its maximum during the last glacial maximum (LGM), when the upwelling obviously weakened for the lowest sea-level and the depression of the Kuroshio. The modern Tsushima warm current began its development since 16 cal ka BP, and the impact of the Kuroshio increased in the middle and northern Okinawa Trough synchronously during the deglaciation and gradually evolved as the main water source of the Tsushima current. The modern Tsushima current finally formed at about 8.5 cal ka BP, since then the circulation structure has been relatively stable. The water of the modern Tsushima current primarily came from the Kuroshio axis. A short-term wiggle of the current occurred at about 3 cal ka BP, probably for the influences from the enhancement of the winter monsoon and the depression of the Kuroshio. The cold water masses greatly strengthened during the wiggle.

Mineral provinces and matter provenance of the surficial sediments in the western Philippine Sea: implication for modern sedimentation in West Pacific marginal basin

The characteristics and distribution patterns of detrital minerals (0.063 similar to 0.125 mm) in marine sediments provide a significant indicator for the identification of the origin of sediment. The detrital mineral composition of 219 surface sediment samples was analysed to identify the distribution of sediments within the western Philippine Sea. The area can be divided into three mineral provinces: ( 1) province east of the Philippine Trench, the detrital minerals in this province are mainly composed of calcareous or siliceous organisms, with the addition of volcanogenic minerals from an adjacent island arc; (II) middle mineral province, clastic minerals including feldspar, quartz and colorless volcanic glass, sourced from seamounts with intermediate-acid volcanic rock, or erupting intermediate-acid volcano; (III) province west of the Palau-Kyushii Ridge, the matter provenance within this province is complex; the small quantity of feldspar and quartz may be sourced from seamounts or erupting volcano with intermediate - acid composition, with a component of volcanic scoria sourced from a volcano erupting on the Palau-Kyushu Ridge. it is suggested that, ( I) Biogenic debris of the study area is closely related to water depth, with the amount of biogenic debris controlled by carbonate lysocline. (2) Volcaniclastic matter derived from the adjacent island are can be entrained by oceanic currents and transported towards the abyssal basin over a short distance. The weathering products of volcanic rocks of the submarine plateau ( e. g. I Benham Plateau) and adjacent ridges provide an important source of detrital sedimentation, and the influence scope of them is constrained by the intensity of submarine weathering. (3) Terrigenous sediments from the continent of Asia and the adjacent Philippine island arc have little influence on the sedimentation of this study area, and the felsic mineral component is probably sourced from volcanic seamounts of intermediate-acid composition.

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.

Characteristics and flux of settling particulate matter in neritic waters: The southern Yellow Sea and the East China Sea

The typology and flux of settling particulate matter (SPM) were investigated based on sediment trap sampling at six typical stations in the Yellow Sea and the East China Sea. The settling particulate matter in the neritic seas was sorted into three categories, lithogenic particles, living organisms, and particle aggregates. The mass of individual organisms is an important portion of particulate matter in the neritic waters. The aggregates contain six types, mucus aggregates, fecal pellets, diatom aggregates, silicoflagellate aggregates, tintinnids, and miscellaneous aggregates, of which the silicoflagellate aggregates and tintinnids are the most abundant in the Yellow Sea and the East China Sea. High particle fluxes, such as 215 to 874 g m(-2). day(-1) SPM in the bottom layer, were found at three stations where the water was well mixed, and the maximum flux was detected in the boundary area between the Yellow Sea and the East China Sea, where a wide nepheloid layer was present. Hence, particle flux in neritic waters can be easily shifted by water turbulence. The net vertical flux (123 to 961 mg C day(-1)), the contribution of lateral advection to resuspension flux (5 to 76%), and the particulate organic carbon export ratio (18 to 60%) were estimated for the other three stations where the water was stratified. The highest values were all found in the upwelling area off the Zhejiang coast, suggesting that the area of high productivity provides a high net vertical flux of SPM. (C) 2010 Elsevier Ltd. All rights reserved.

Observational evidence of the Yellow Sea warm current

The Yellow Sea Warm Current (YSWC) is one of the principal currents in the Yellow Sea in winter. Former examinations on current activity in the Yellow Sea have not observed a stable YSWC because of the positioning of current meters. To further understand the YSWC, a research cruise in the southern Yellow Sea was carried out in the winter of 2006/2007. Five moorings with bottom-mounted acoustic Doppler current profilers (ADCP) were deployed on the western side of the central trough of the Yellow Sea. The existence and distributional features of the YSWC were studied by analyzing three ADCP moorings in the path of the YSWC in conjunction with conductivity-temperature-depth (CTD) data over the observed area in the southern Yellow Sea. The results show the following. (1) The upper layer of the YSWC is strongly influenced by winter cold surge; its direction and speed often vary along a south-north axis when strong cold surges arrive from the north. (2) The YSWC near the bottom layer is a stable northwest flowing current with a speed of 4 to 10 cm/s. By combining the analyses of the CTD data, we speculate that the core of the YSWC may lie near the bottom. (3) On a monthly average timescale, the YSWC is stably oriented with northward flow from the sea surface to the sea floor.

Variations in the eastern Indian Ocean warm pool and its relation to the dipole in the tropical Indian Ocean

Based on the monthly average SST and 850 hPa monthly average wind data, the seasonal, interannual and long-term variations in the eastern Indian Ocean warm pool (EIWP) and its relationship to the Indian Ocean Dipole (IOD), and its response to the wind over the Indian Ocean are analyzed in this study. The results show that the distribution range, boundary and area of the EIWP exhibited obviously seasonal and interannual variations associated with the ENSO cycles. Further analysis suggests that the EIWP had obvious long-term trend in its bound edge and area, which indicated the EIWP migrated westwards by about 14 longitudes for its west edge, southwards by about 5 latitudes for its south edge and increased by 3.52x10(6) km(2) for its area, respectively, from 1950 to 2002. The correlation and composite analyses show that the anomalous westward and northward displacements of the EIWP caused by the easterly wind anomaly and the southerly wind anomaly over the eastern equatorial Indian Ocean played an important and direct role in the formation of the IOD.