Impact of Carbon Dioxide Pressurization on Liquid Phase Organic Reactions: A Case Study on Heck and Diels–Alder Reactions

Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa;

Oxidation of cyclohexane - A significant impact of stainless steel reactor wall

The selective oxidation of cyclohexane to cyclohexanol and cyclohexanone is an important chemical process and it has been paid more attentions recently. In the present work, the stainless steel reactor wall was found to influence the selective oxidation of cyclohexane very significantly, and a quasi-crystalline Ti45Zr35Ni17Cu3 alloy with the similar compositions as the reactor wall was used as a catalyst for the cyclohexane oxidation, as expected, a higher activity was obtained with it. The present results open up a new avenue for developing new catalyst for alkane oxidation.

Impact of Brunswick river mouth training walls on adjacent beaches, Brunswick heads, New South Wales, Australia

River training walls have been built at scores of locations along the NSW coast and their impacts on shoreline change are still not fully understood. In this study, the Brunswick River entrance and adjacent beaches are selected for examination of the impact of the construction of major training walls. Thirteen sets of aerial photographs taken between 1947 and 1994 are used in a CIS approach to accurately determine tire shoreline Position, beach contours and sand volumes, and their changes in both time and space, and then to assess the contribution of both tire structures and natural hydrodynamic conditions to large scale (years-decades and kilometres) beach changes. The impact of the training walls can be divided into four stages: natural conditions prior to their construction (pre 1959), major downdrift erosion and updrift accretion during and. following the construction of the walls in 1959 similar to 1962 and 1966. diminishing impact of the walls between 1966 and 1987, and finally no apparent impact between 1987 similar to 1994. The impact extends horizontally about 8 km updrift and 17 km downdrift, and temporally up to 25 years..

Impact of difference accuracy on computational properties of vertical grids for a nonhydrostatic model

Starting from nonhydrostatic Boussinesq approximation equations, a general method is introduced to deduce the dispersion relationships. A comparative investigation is performed on inertia-gravity wave with horizontal lengths of 100, 10 and 1 km. These are examined using the second-order central difference scheme and the fourth-order compact difference scheme on vertical grids that are currently available from the perspectives of frequency, horizontal and vertical component of group velocity. These findings are compared to analytical solutions. The obtained results suggest that whether for the second-order central difference scheme or for the fourth-order compact difference scheme, Charny-Phillips and Lorenz ( L) grids are suitable for studying waves at the above-mentioned horizontal scales; the Lorenz time-staggered and Charny-Phillips time staggered (CPTS) grids are applicable only to the horizontal scales of less than 10 km, and N grid ( unstaggered grid) is unsuitable for simulating waves at any horizontal scale. Furthermore, by using fourth-order compact difference scheme with higher difference precision, the errors of frequency and group velocity in horizontal and vertical directions produced on all vertical grids in describing the waves with horizontal lengths of 1, 10 and 100 km cannot inevitably be decreased. So in developing a numerical model, the higher-order finite difference scheme, like fourth-order compact difference scheme, should be avoided as much as possible, typically on L and CPTS grids, since it will not only take many efforts to design program but also make the calculated group velocity in horizontal and vertical directions even worse in accuracy.

Impact of spatial resolution and spatial difference accuracy on the performance of Arakawa A-D grids

This paper alms at illustrating the impact of spatial difference scheme and spatial resolution on the performance of Arakawa A-D grids in physical space. Linear shallow water equations are discretized and forecasted on Arakawa A-D grids for 120-minute using the ordinary second-order (M and fourth-order (C4) finite difference schemes with the grid spacing being 100 km, 10 km and I km, respectively. Then the forecasted results are compared with the exact solution, the result indicates that when the grid spacing is I kin, the inertial gravity wave can be simulated on any grid with the same results from C2 scheme or C4 scheme, namely the impact of variable configuration is neglectable; while the inertial gravity wave is simulated with lengthened grid spacing, the effects of different variable configurations are different. However, whether for C2 scheme or for C4 scheme, the RMS is minimal (maximal) on C (D) grid. At the same time it is also shown that when the difference accuracy increases from C2 scheme to C4 scheme, the resulted forecasts do not uniformly decrease, which is validated by the change of the group A velocity relative error from C2 scheme to C4 scheme. Therefore, the impact of the grid spacing is more important than that of the difference accuracy on the performance of Arakawa A-D grid.

Analysis of the sea-level variability along the Chinese coast and estimation of the impact of a CO2-perturbed atmospheric circulation

The relationship between monthly sea-level data measured at stations located along the Chinese coast and concurrent large-scale atmospheric forcing in the period 1960-1990 is examined. It is found that sea-level varies quite coherently along the whole coast, despite the geographical extension of the station set. A canonical correlation analysis between sea-level and sea-level pressure (SLP) indicates that a great part of the sea-level variability can be explained by the action of the wind stress on the ocean surface. The relationship between sea-level and sea-level pressure is analyzed separately for the summer and winter half-years. In winter, one factor affecting sea-level variability at all stations is the SLP contrast between the continent and the Pacific Ocean, hence the intensity of the winter Monsoon circulation. Another factor that affects coherently all stations is the intensity of the zonal circulation at mid-latitudes. In the summer half year, on the other hand, the influence of SLP on sea-level is spatially less coherent: the stations in the Yellow Sea are affected by a more localized circulation anomaly pattern, whereas the rest of the stations is more directly connected to the intensity of the zonal circulation. Based on this analysis, statistical models (different for summer and winter) to hindcast coastal sealevel anomalies from the large-scale SLP field are formulated. These models have been tested by fitting their internal parameters in a test period and reproducing reasonably the sea-level evolution in an independent period. These statistical models are also used to estimate the contribution of the changes of the atmospheric circulation on sea-level along the Chinese coast in an altered climate. For this purpose the ouput of 150 year-long experiment with the coupled ocean-atmosphere model ECHAM1-LSG has been analyzed, in which the atmospheric concentration of greenhouse gases was continuously increased from 1940 until 2090, according to the Scenario A projection of the Intergovermental Panel on Climate Change. In this experiment the meridional (zonal) circulation relevant for sea-level tends to become weaker (stronger) in the winter half year and stronger (weaker) in summer. The estimated contribution of this atmospheric circulation changes to coastal sea-level is of the order of a few centimeters at the end of the integration, being in winter negative in the Yellow Sea and positive in the China Sea with opposite signs in the summer half-year.

Experimental study on the impact of dinoflagellate Alexandrium species on populations of the rotifer Brachionus plicatilis

To investigate harmful effects of the dinoflagellate Alexandrium species on microzooplankton, the rotifer Brachionus plicatilis was chosen as an assay species, and tested with 10 strains of Alexandrium including one known non-PSP-producer (Alexandrium tamarense, AT-6). HPLC analysis confirmed the PSP-content of the various strains: Alexandrium lusitanicum, Alexandrium minutum and Alexandrium tamarense (ATHK, AT5-1, AT5-3, ATC102, ATC103) used in the experiment were PSP-producers. No PSP toxins were detected in the strains Alexandrium sp1, Alexandrium sp2. Exposing rotifer populations to the densities of 2000 cells ml(-1) of each of these 10 Alexandrium strains revealed that the (non-PSP) A. tarnarense (AT-6) and two other PSP-producing algae: A. lusitanicum, A. minutum, did not appear to adversely impact rotifer populations. Rotifers exposed to these three strains were able to maintain their population numbers, and in some cases, increase them. Although some increases in rotifer population growth following exposures to these three algal species were noted, the rate was less than for the non-exposed control rotifer groups. In contrast, the remaining seven algal strains (A. tamarense ATHK, AT5-1, AT5-3, ATC102, ATC103; also Alexandrium sp1 and Alexandrium sp2) all have adverse effects on the rotifers. Dosing rotifers with respective algal cell densities of 2000 cells ml-1 each, for Alexandrium spl, Alexandrium sp2, and A. tamarense strains ATHK and ATC103 showed mean lethal time (LT50) on rotifer populations of 21, 28, 29, and 36h, respectively. The remaining three species (A. tamarense strains AT5-1, AT5-3, ATC102) caused respective mean rotifer LT50S of 56, 56, and 71 h, compared to 160 h for the unexposed "starved control" rotifers. Experiments to determine ingestion rates for the rotifers, based on changes in their Chlorophyll a content, showed that the rotifers could feed on A. lusitanicum, A. minutum and A. tamarense strain AT-6, but could graze to little or no extent upon algal cells of the other seven strains. The effects on rotifers exposed to different cell densities, fractions, and growth phases of A. tamarense algal culture were respectively compared. It was found that only the whole algal cells had lethal effects, with strongest impact being shown by the early exponential growth phase of A. tamarense. The results indicate that some toxic mechanism(s), other than PSP and present in whole algal cells, might be responsible for the adverse effects on the exposed rotifers. (C) 2004 Elsevier B.V. All rights reserved.

Grazing impact of copepods on phytoplankton in the Bohai Sea

During spring (April/May 1999) and autumn (September/October 1998) cruises in the Bohai Sea, China, copepods were the dominant components of mesozooplankton, the most abundant species being Calanus sinicus, Centropages mcmurrichi, Paracalanus parvus, Acartia bifilosa and Oithona similis. Pigment ingestion rates by three size classes of copepods (200-500, 500-1000 and > 1000 mum) were measured. In the south of the investigation area, gut pigment content (GPC), individual pigment-specific ingestion rates and grazing impacts on phytoplankton were lower in spring than in autumn. In the central area, GPC and individual pigment-specific ingestion rates were higher in spring than in autumn. The grazing impact on phytoplankton by the copepod assemblages was lower in spring than in autumn, however, because of the relatively smaller biomass in spring. In the western area where the Bohai Sea joins the Yellow Sea, GPC, individual pigment-specific ingestion rates and grazing impacts on phytoplankton were higher in spring than in autumn. Among the three size groups, the small-sized animals (200-500 mum) contributed more than 50% (range 38-98%) of the total copepod grazing during both cruises. The grazing impact on phytoplankton by copepods was equivalent to 11.9% (range 3.0-37.1%) of the chlorophyll-a standing stock and 53.3% (range 21.4-91.4%) of the primary production during the spring cruise. Grazing impact was equivalent to 6.3% (range 2.0-11.6%) of the chlorophyll-a standing stock and >100% (range 25.7-141.6%) of the primary production during the autumn cruise. The copepod community apparently consumed only a modest proportion of the standing stock of phytoplankton during spring and autumn blooms. They did, however, sometimes graze a significant proportion of daily primary production and hence were presumably able to limit the rate of further accumulation of phytoplankton, or even to prevent it. (C) 2003 Elsevier Ltd. All rights reserved.