Catalytic ethanolysis of soybean oil with immobilized lipase from Candida antarctica and (1)H NMR and GC quantification of the ethyl esters (biodiesel) produced

The catalytic ethanolysis of soybean oil with commercial immobilized lipase type B from Candida antarctica to yield ethyl esters (biodiesel) has been investigated. Transesterification was monitored with respect to the following parameters: quantity of biocatalyst, reaction time, amount of water added and turnover of lipase. The highest yields of biodiesel (87% by (1)H NMR; 82.9% by GC) were obtained after a reaction time of 24 h at 32 degrees C in the presence of lipase equivalent to 5.0% (w/w) of the amount of soybean oil present. The production of ethyl esters by enzymatic ethanolysis was not influenced by the addition of water up to 4.0% (v/v) of the alcohol indicating that it is possible to use hydrated ethanol in the production of biodiesel catalyzed by lipase. The immobilized enzyme showed high stability under moderate reaction conditions and retained its activity after five production cycles. The (1)H NMR methodology elaborated for the quantification of biodiesel in unpurified reaction mixtures showed good correlations between the signal areas of peaks associated with the alpha-methylene groups of the ethyl esters and those of the triacyl-glycerides in residual soybean oil. Monoacylglycerides, diacylglycerides and triglycerides could also be detected and quantified in the crude biodiesel using (1)H NMR spectroscopic and GC-FID chromatographic methods. The biodiesel production by enzymatic catalysis was promising. In this case, was produced a low concentration of glycerol (0.74%) and easily removed by water extraction. (C) 2010 Elsevier B.V. All rights reserved.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Epiphytic bryophytes of Dicksonia antarctica Labill. from selected pockets of cool temperate rainforest, Central Highlands, Victoria

Epiphytic bryophytes of the Soft Tree-fern Dicksonia antarctica Labill. were examined in four Cool Temperate Rainforest pockets of the Central Highlands of Victoria. Thirty-two species, 17 mosses and 15 liverworts, were noted. There was no distinction in species assemblage between the north and south side of tree-ferns although bryophytes occurred on the south side of more tree-ferns than they did on the north side.

Production of Omega-3 Triacylglycerol concentrates using a new food grade immobilized Candida antarctica Lipase B

Triacylglycerol concentrates of eicosapentaenoic and docosahexaenoic omega-3 fatty acids were synthesized either via transesterification or esterification of glycerol with the corresponding ethyl ester or free fatty acid concentrates, respectively. A newly developed food grade immobilized Candida antarctica lipase Β system using an Amberlite FPX-66 hydrophobic matrix, was compared with a commercially available non-food grade commercial system, for their ability to catalyze these reactions. For either system, the transesterification required higher temperature (90◦C) than esterification (70°C) to achieve maximum triacylglycerol yields. The newly developed immobilized system efficiently catalyzes the esterification of free fatty acids with glycerol and differs from the existing commercial system in that it is food grade and has a more uniform and larger particle distribution. The new system significantly improves flow in a packed bed reactor, enabling multiple reuse of the catalyst for up to 80 repeats.

Environmental impact assessment of the sewage outfall at Davis Station, East Antarctica

During the summer 2009/10, an environmental impact assessment of the sewage outfall was conducted at Davis Station, East Antarctica. An investigation of the nature and extent of impacts to the marine environment associated with current sewage treatment and effluent discharge practices included ecological surveys of macrobiological communities, physico-chemical analysis of sediments and receiving waters, microbiological analysis, and histopathological analysis of fish. Ecotoxicological testing using local invertebrates to determine effluent toxicity was interpreted alongside dispersal modelling data of the discharge plume to determine the potential extent of impacts and inform recommendations on the level of treatment and dilution of sewage required to minimise impacts. No evidence of impacts was detected on soft sediment infaunal or epifaunal communities, and only low levels of contamination and accumulation were found in sediments and waters in the immediate vicinity of the outfall and in the direction of primary current flow. In contrast, sterol biomarkers and faecal coliforms (E. coli) were detected in sediments collected adjacent to the outfall and in most water column samples. Marine invertebrates (Abatus and Laternula) also tested positive for E. coli and antibiotic resistance mechanisms were present in Laternula indicating the introduction and dispersal through the water column of foreign microbes and bacteria associated with human effluent. Fish (Trematomus bernacchii) close to the outfall showed significant histological alterations in all major tissues (liver, gill, gonad, muscle) resulting from exposure to sewage. Effluent was toxic to amphipods (Paramoera walkeri) and microgastropods (Skenella paludionoides), with reduced survival in concentrations as low as 3.125% over a 21d exposure period. Acute effects were also observed in both species following 24h exposure, with 100% mortality at the highest effluent concentrations tested (68%). The application of these results to support and guide decisions regarding the planned installation of new sewage treatment facilities at Davis will be discussed.

Histological alterations in the Antarctic cod, Trematomus bernacchii from Davis Station, East Antarctica

During the summer season 2009/10, a comprehensive environmental impact assessment of the sewage discharge was conducted at Davis Station in the Vestfold Hills region of East Antarctica. As part of this project, a survey of the histology of liver, gill, gonad and muscle tissues in the Antarctic rock cod Trematomus bernacchii from nearshore sites in the receiving environment close to Davis Station in was completed. Fish from 4 sites were examined; 1 site adjacent to the Davis Station sewage outfall (within 500 m of the point of discharge), 2 sites approximately 2 km from the outfall (Anchorage Island and Antennae farm), and 1 site approximately 10 km away from the outfall and adjacent to an Adelie penguin population (Kazak Island). All fish sampled from the sewage outfall site exhibited significant histological alterations in all major tissues. Fish from the other 3 sites showed some alterations in either gill and/or liver tissues. Pathological abnormalities present in all fish collected near the sewage outfall included: extensive multifocal cysts of unknown etiology with necrotic liquification; multifocal granuloma with associated inflammation; coagulative necrosis in the liver; and lamellar hyperplasia with associated proliferation and lamella fusion of the gills. Results of this work form part of a weight of evidence approach alongside ecological monitoring, chemical analysis, ecotoxicological testing and dispersal modelling of the discharge plume which is being used to inform and direct upgrades to the Australian Antarctic Divisions operations and current sewage discharge practises at Davis Station.

Hybridization of Southern Hemisphere blue whale subspecies and a sympatric area off Antarctica : impacts of whaling or climate change?

Understanding the degree of genetic exchange between subspecies and populations is vital for the appropriate management of endangered species. Blue whales (Balaenoptera musculus) have two recognized Southern Hemisphere subspecies that show differences in

Direct evidence of histopathological impacts of wastewater discharge on resident Antarctic fish (Trematomus bernacchii) at Davis Station, East Antarctica.

During the 2009/2010 summer, a comprehensive environmental impact assessment (EIA) of the wastewater discharge at Davis Station, East Antarctica was completed. As part of this, histological alteration of gill and liver tissue in Antarctic Rock-cod (Trematomus bernacchii) from four sites along a spatial gradient from the wastewater outfall were assessed. All fish within 800 m of the outfall exhibited significant histological changes in both tissues. Common pathologies observed in fish closest to the outfall include proliferation of epithelial cells with associated secondary lamellar fusion in the gills and multifocal granulomata with inflammation and necrosis as well as cysts in the liver. Fish from sites >800 m from the outfall also exhibited alterations but to a lesser degree, with prevalence and severity decreasing with increasing distance from the outfall. This study highlights the value of histopathological investigations as part of EIAs and provides the first evidence of sub-lethal alteration associated with wastewater discharge in East Antarctica.

Tracking spatial distribution of human-derived wastewater from Davis Station, East Antarctica, using δ15N and δ13C stable isotopes.

Stable isotope ratios, δ15N and δ13C were effectively used to determine the geographical dispersion of human derived sewage from Davis Station, East Antarctica, using Antarctic rock cod (Trematomus bernacchii). Fish within 0-4km downstream of the outfall exhibited higher δ15N and δ13C values relative to reference sites. Nitrogen in particular showed a stepped decrease in δ15N with increasing distance from the discharge point by 1-2‰. Stable isotopes were better able to detect the extent of wastewater contamination than other techniques including faecal coliform and sterol measures. Uptake and assimilation of δ15N and δ13C up to 4km from the outfall adds to growing evidence indicating the current level of wastewater treatment at Davis Station is not sufficient to avoid impact to the surrounding environment. Isotopic assimilation in T. bernacchii is a viable biomarker for investigation of initial sewage exposure and longer term monitoring in the future.

Application of a quantitative histological health index for Antarctic rock cod (Trematomus bernacchii) from Davis Station, East Antarctica

A quantitative Histological Health Index (HHI) was applied to Antarctic rock cod (Trematomus bernacchii) using gill, liver, spleen, kidney and gonad to assess the impact of wastewater effluent from Davis Station, East Antarctica. A total of 120 fish were collected from 6 sites in the Prydz Bay region of East Antarctica at varying distances from the wastewater outfall. The HHI revealed a greater severity of alteration in fish at the wastewater outfall, which decreased stepwise with distance. Gill and liver displayed the greatest severity of alteration in fish occurring in close proximity to the wastewater outfall, showing severe and pronounced alteration respectively. Findings of the HHI add to a growing weight of evidence indicating that the current level of wastewater treatment at Davis Station is insufficient to prevent impact to the surrounding environment. The HHI for T. bernacchii developed in this study is recommended as a useful risk assessment tool for assessing in situ, sub-lethal impacts from station-derived contamination in coastal regions throughout Antarctica.

A new fossil Adamussium (Bivalvia: Pectinidae) from Antarctica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Deformational evolution of a Cretaceous subduction complex: Elephant Island, South Shetland Islands, Antarctica

New structural data from Elephant Island and adjacent islands are presented with the objective to improve the understanding of subduction kinematics in the area northeast of the Antarctic Peninsula. on the island, a first deformation phase, D-1, produced a strong SL fabric with steep stretching and mineral lineations, partly defined by relatively high pressure minerals, such as crossite and glaucophane. D-1 is interpreted to record southward subduction along an E-W trench with respect to the present position of the island. A second phase, D-2, led to intense folding with steep E-W-trending axial surfaces. The local presence of sinistral C'-type sheer bands related to this phase and the oblique inclination of the L-2 stretching lineations are the main arguments to interpret this phase as representing oblique sinistral transpressive shear along steep, approximately E-W-trending shear zones, with the northern (Pacific) block going down with respect to the southern (Antarctic Peninsula) block. The sinistral strike-slip component may represent a trench-linked strike-slip movement as a consequence of oblique subduction. Lithostatic pressure decreased and temperature increased to peak values during D-2, interpreted to represent the collision of thickened oceanic crust with the active continental margin. The last deformation phase, D-3, is characterised by post-metamorphic kink bands, partially forming conjugate sets consistent with E-W shortening and N-S extension. The rock units that underlie the island probably rotated during D-3, in Cenozoic times, together with the trench, from an NE-SW to the present ENE-WSW position, during the progressive opening of the Scotia Sea. The similarity between the strain orientation of D-3 and that of the sinistral NE-SW Shackleton Fracture Zone is consistent with this interpretation. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Metamorphic evolution of a subduction complex, South Shetland Islands, Antarctica

A subduction complex composed of ocean floor material mixed with arc-derived metasediments crops out in the Elephant Island group and at Smith Island, South Shetland Islands, Antarctica, with metamorphic ages of 120-80 Ma and 58-47 Ma? respectively. Seven metamorphic zones (I-VII) mapped on Elephant Island delineate a gradual increase in metamorphic grade from the pumpellyite-actinolite facies, through the crossite-epidote blueschist facies, to the lower amphibolite facies. Geothermometry in garnet-amphibole and garnet-biotite pairs yields temperatures of about 350 degrees C in zone III to about 525 degrees C in zone VII. Pressures were estimated on the basis of Si content in white mica, Al2O3 content in alkali amphibole, Na-M4/Al-IV in sodic-calcic and calcic amphibole, Al-VI/Si in calcic amphibole, and jadeite content in clinopyroxene. Mean values vary from about 6-7.5 kbar in zone II to about 5 kbar in zone VII. Results from the other islands of the Elephant Island group are comparable to those from the main island; Smith Island yielded slightly higher pressures, up to 8 kbar, with temperatures estimated between 300 and 350 degrees C. Zoned minerals and other textural indications locally enable inference of P-T-t trajectories, all with a clockwise evolution. A reconstruction in space and time of these P-T-t paths allows an estimate of the thermal structure in the upper crust during the two ductile deformation phases (D-1 & D-2) that affected the area. This thermal structure is in good agreement with the one expected for a subduction zone. The arrival and collision of thickened oceanic crust may have caused the accretion and preservation of the subduction complex. In this model, D-1 represents the subduction movements expressed by the first vector of the clockwise P-T-t path, D-2 reflects the collision corresponding to the second vector with increasing temperature and decreasing pressure, and D-3 corresponds to isostatic uplift accompanied by erosion, under circumstances of decreasing temperature and pressure.