New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

The Global Plankton Database: an inventory and data from the Former Soviet Union expeditions

At present time, there is a lack of knowledge on the interannual climate-related variability of zooplankton communities of the tropical Atlantic, central Mediterranean Sea, Caspian Sea, and Aral Sea, due to the absence of appropriate databases. In the mid latitudes, the North Atlantic Oscillation (NAO) is the dominant mode of atmospheric fluctuations over eastern North America, the northern Atlantic Ocean and Europe. Therefore, one of the issues that need to be addressed through data synthesis is the evaluation of interannual patterns in species abundance and species diversity over these regions in regard to the NAO. The database has been used to investigate the ecological role of the NAO in interannual variations of mesozooplankton abundance and biomass along the zonal array of the NAO influence. Basic approach to the proposed research involved: (1) development of co-operation between experts and data holders in Ukraine, Russia, Kazakhstan, Azerbaijan, UK, and USA to rescue and compile the oceanographic data sets and release them on CD-ROM, (2) organization and compilation of a database based on FSU cruises to the above regions, (3) analysis of the basin-scale interannual variability of the zooplankton species abundance, biomass, and species diversity.

Abiotic characteristics and diatom abundance and biomass in different sectors of the Argentinien Shelf and antartic waters

A large spatial scale study of the diatom species inhabiting waters from the subantarctic (Argentine shelf) to antarctic was made for the first time in order to understand the relationships between these two regions with regard to the fluctuations in diatom abundances in relation with environmental features, their floristic associations and the effect of the Polar Front as a biogeographic barrier. Species-specific diatom abundance, nutrient and chlorophyll-a concentration were assessed from 64 subsurface oceanographic stations carried out during the austral summer 2002, a period characterized by an anomalous sea-ice coverage corresponding to a ''warm year". Significant relationships of both diatom density and biomass with chlorophyll-a (positive) and water temperature (negative) were found for the study area as a whole. Within the Subantarctic region, diatom density and biomass values were more uniform and significantly (in average: 35 and 11 times) lower than those of the Antarctic region, and did not correlate with chlorophyll-a. In antarctic waters, instead, biomass was directly related with chlorophyll-a, thus confirming the important contribution of diatoms to the Antarctic phytoplanktonic stock. A total of 167 taxa were recorded for the entire study area, with Chaetoceros and Thalassiosira being the best represented genera. Species richness was maximum in subantarctic waters (46; Argentine shelf) and minimum in the Antarctic region (21; Antarctic Peninsula), and showed a significant decrease with latitude. Floristic associations were examined both qualitatively (Jaccard Index) and quantitatively (correlation) by cluster analyses and results allowed differentiating a similar number of associations (12 vs. 13, respectively) and two main groups of stations. In the Drake Passage, the former revealed that the main floristic change was found at the Polar Front, while the latter reflected the Southern ACC Front as a main boundary, and yielded a higher number of isolated sites, most of them located next to different Antarctic islands. Such differences are attributed to the high relative density of Fragilariopsis kerguelensis in Argentine shelf and Drake Passage waters and of Porosira glacialis and species of Chaetoceros and Thalasiosira in the Weddell Sea and near the Antarctic Peninsula. From a total of 84 taxa recorded in antarctic waters, only 17 were found exclusively in this region, and the great majority (67) was also present in subantarctic waters but in extremely low (< 1 cell/l) concentrations, probably as a result of expatriation processes via the ACC-Malvinas Current system. The present results were compared with those of previous studies on the Antarctic region with respect to both diatom associations in regular vs. atypically warm years, and the distribution and abundance of some selected planktonic species reported for surface sediments.

Biomass fire consumption and carbon release rates of rainforest-clearing experiments conducted in northern Mato Grosso, Brazil

Biomass consumption and carbon release rates during the process of forest clearing by fire in five test plots are presented and discussed. The experiments were conducted at the Caiabi Farm near the town of Alta Floresta, state of Mato Grosso, Brazil, in five square plots of 1 ha each designated A, B, C, D, and E, with different locations and timing of fire. Plot A was located in the interface with a pasture, with three edges bordering on the forest, and was cut and burned in 1997. Plots B,C, D, and E were located inside the forest. Plot B was cut and burned in 1997. Plot C was inside a deforested 9-ha area, which was cut and burned in 1998. Plot D was inside a deforested 4-ha area, which was cut in 1998 and burned in 1999. Plot E was inside a deforested 4-ha area which was cut and burned in 1999. Biomass consumption was 22.7%, 19.5%, 47.5%, 61.5% and 41.8%, for A, B, C, D, and E, respectively. The effects of an extended curing period and of increasing the deforested area surrounding the plots could be clearly observed. The consumption for areas cut and burned during the same year, tended toward a value of nearly 50% when presented as a function of the total area burned. The aboveground biomass of the test site and the amount of carbon before the fire were 496 Mg ha-1 and 138 Mg ha-1, respectively. Considering that the biomass that remains unburned keeps about the same average carbon content of fresh biomass, which is supported by the fact that the unburned material consists mainly of large logs and considering the value of 50% for consumption, the amount of carbon released to the atmosphere as gases was 69 Mg ha-1. The amounts of CO2 and CO released to the atmosphere by the burning process were then estimated as 228 Mg ha-1 and 15.9 Mg ha-1, respectively. Observations on fire propagation and general features of the slash burnings in the test areas complete the paper. Copyright 2001 by the American Geophysical Union.

Planktonic and benthic stables Isotopes, age model and carbon analysis of HUD91/039 from the northernmost Baffin Bay

A multiproxy study of palaeoceanographic and climatic changes in northernmost Baffin Bay shows that major environmental changes have occurred since the deglaciation of the area at about 12 500 cal. yr BP. The interpretation is based on sedimentology, benthic and planktonic foraminifera and their isotopic composition, as well as diatom assemblages in the sedimentary records at two core sites, one located in the deeper central part of northernmost Baffin Bay and one in a separate trough closer to the Greenland coast. A revised chronology for the two records is established on the basis of 15 previously published AMS 14C age determinations. A basal diamicton is overlain by laminated, fossil-free sediments. Our data from the early part of the fossiliferous record (12 300 - 11 300 cal. yr BP), which is also initially laminated, indicate extensive seasonal sea-ice cover and brine release. There is indication of a cooling event between 11 300 and 10 900 cal. yr BP, and maximum Atlantic Water influence occurred between 10 900 and 8200 cal. yr BP (no sediment recovery between 8200 and 7300 cal. yr BP). A gradual, but fluctuating, increase in sea-ice cover is seen after 7300 cal. yr BP. Sea-ice diatoms were particularly abundant in the central part of northernmost Baffin Bay, presumably due to the inflow of Polar waters from the Arctic Ocean, and less sea ice occurred at the near-coastal site, which was under continuous influence of the West Greenland Current. Our data from the deep, central part show a fluctuating degree of upwelling after c. 7300 cal. yr BP, culminating between 4000 and 3050 cal. yr BP. There was a gradual increase in the influence of cold bottom waters from the Arctic Ocean after about 3050 cal. yr BP, when agglutinated foraminifera became abundant. A superimposed short-term change in the sea-surface proxies is correlated with the Little Ice Age cooling.