Quaternary pollen analysis: recent progress in palaeoecology and palaeoclimatology

During the last decade Quaternary pollen analysis has developed towards improved pollen-taxonomical precision, automated pollen identification and more rigorous definition of pollen assemblage zones. There have been significant efforts to model the spatial representation of pollen records in lake sediments which is important for more precise interpretation of the pollen records in terms of past vegetation patterns. We review the difficulties in matching modelled post-glacial plant migration patterns with pollen-based palaeorecords and discuss the potential of DNA analysis of pollen to investigate the ancestry and past migration pathways of the plants. In population ecology there has been an acceleration of the widely advocated conceptual advance of pollen-analytical research from vaguely defined ‘environmental reconstructions’ towards investigating more precisely defined ecological problems aligned with the current ecological theories. Examples of such research have included an increasing number of investigations about the ecological impacts of past disturbances, often integrating pollen records with other palaeoecological data. Such an approach has also been applied to incorporate a time perspective to the questions of ecosystem restoration, nature conservation and forest management. New lines of research are the use of pollen analysis to study long-term patterns of vegetation diversity, such as the role of glacial-age vegetation fragmentation as a cause of Amazonian rain forest diversity, and to investigate links between pollen richness and past plant diversity. Palaeoclimatological use of pollen records has become more quantitative and has included more precise and rigorous testing of pollen-climate calibration models with modern climate data. These tests show the approximate nature of the models and warn against a too straightforward climatic interpretation of the small-scale variation in reconstructions. Pollenbased climate reconstructions over the Late Glacial–early Holocene boundary have indicated that pollen-stratigraphical changes have been rapid with no evidence for response lags. This does not rule out the possibility of migrational disequilibrium, however, as the rapid changes may be mostly due to nonmigrational responses of existing vegetation. It is therefore difficult to assess whether the amplitude of reconstructed climate change reflects real climate change. Other outstanding problems remain the obscure relationship of pollen production and climate, the role of human impact and other nonclimatic factors, and nonanalogue situations.

New ways to break an old bond: the bacterial carbon-phosphorus hydrolases and their role in biogeochemical phosphorus cycling

Phosphonates are organophosphorus molecules that contain the highly stable C-P bond, rather than the more common, and more labile, C-O-P phosphate ester bond. They have ancient origins but their biosynthesis is widespread among more primitive organisms and their importance in the contemporary biosphere is increasingly recognized; for example phosphonate-P is believed to play a particularly significant role in the productivity of the oceans. The microbial degradation of phosphonates was originally thought to occur only under conditions of phosphate limitation, mediated exclusively by the poorly characterized C-P lyase multienzyme system, under Pho regulon control. However, more recent studies have demonstrated the Pho-independent mineralization by environmental bacteria of three of the most widely distributed biogenic phosphonates: 2-aminoethylphosphonic acid (ciliatine), phosphonoacetic acid, and 2-amino-3-phosphonopropionic acid (phosphonoalanine). The three phosphonohydrolases responsible have unique specificities and are members of separate enzyme superfamilies; their expression is regulated by distinct members of the LysR family of bacterial transcriptional regulators, for each of which the phosphonate substrate of the respective degradative operon serves as coinducer. Previously no organophosphorus compound was known to induce the enzymes required for its own degradation. Whole-genome and metagenome sequence analysis indicates that the genes encoding these newly described C-P hydrolases are distributed widely among prokaryotes. As they are able to function under conditions in which C-P lyases are inactive, the three enzymes may play a hitherto-unrecognized role in phosphonate breakdown in the environment and hence make a significant contribution to global biogeochemical P-cycling.

Uptake of carbon, nitrogen and phosphorus by phytoplankton along the 20 degrees W meridian in the NE Atlantic between 57.5 degrees N and 37 degrees N

Phytoplankton biomass and rate of production were measured along a transect from 57.54 degreesN to 37.01 degreesN in the northeast Atlantic during July 1996 and at a series of stations over a 7-day period at 37 degreesN 20 degreesW. Surface nutrient concentrations ranged from 4 mu mol l(-1) NO3-, and 0.35 mu mol l(-1) PO43- at 57.54 degreesN to <10 nmol l(-1) NO3- and similar to 10 nmol l(-1) PO43- at 37.01 degreesN. The greatest phytoplankton biomass and production were measured in the vicinity of a frontal system at 50 degreesN, and there was a general decline in total phytoplankton biomass and production to the south of the transect. Production was measured in three size fractions. At the station with the highest chlorophyll concentrations (50.34 degreesN), phytoplankton cells larger than 5 mum dominated the assemblage, accounting for 72% of the chlorophyll concentration (22.9 mg m(-2)) and 51% of primary production (54.1 mmol Cm-2 d(-1)), but picophytoplankton production was also high (43%). At 57 degreesN, carbon fixation by the > 5 mum fraction accounted for 75% of the daily production of 60.75 mmol Cm-2 d(-1). At 37 degreesN, picophytoplankton was the dominant group, accounting for similar to 58% (10 mg m(-2)) of chlorophyll and similar to 64% (46 mmol Cm-2 d(-1)), of primary production. Nitrate, ammonium and phosphate uptake rates also were determined. Although high nitrate uptake rates were measured in the surface water at similar to 50 degreesN, the greatest uptake rates of both depth-integrated nitrate and ammonium were at the south of the transect. At 37 degreesN, a deep euphotic zone was present and light penetrated through the nitracline; total nitrate uptake was enhanced because of assimilation at the base of the euphotic zone. As a consequence, high values of depth-integrated f-ratio were measured in the oligotrophic waters at the south of the transect. Phosphate was predominantly incorporated into the picoplankton fraction, which included heterotrophic and autotrophic components, at all stations and a significant proportion of phosphate uptake occurred in the dark. The C:N:P assimilation ratios were variable throughout the region; phosphate uptake was generally greater than would be expected if nutrient assimilation were in proportion to the Redfield ratio. (C) 2001 Elsevier Science Ltd. All rights reserved.

Alternating copolymerisation of styrene and carbon monoxide in ionic liquids

Room temperature ionic liquids have been used as solvents for the palladium-catalysed copolymerisation of styrene and carbon monoxide. The behaviour of various ionic liquids, the nature and concentration of palladium catalyst, and the reusability of the catalyst-ionic liquid system are discussed. The effects of cation, anion and alkyl chain length of the ionic liquids on the reaction are also addressed. The yield of the polyketone in the ionic liquid systems is enhanced over conventional solvents studied under similar conditions.

Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Adsorption Characteristics of Reactive Dyes in Columns of Activated Carbon

Abstract: Adsorption behaviour of reactive dyes in fixed-bed adsorber was evaluated in this work. The characteristics of mass transfer zone (MTZ), where adsorption in column occurs, were affected by carbon bed depth and influent dye concentration. The working lifetime (t(x)) of MTZ, the height of mass transfer zone (HMTZ), the rate of mass transfer zone (RMTZ), and the column capacity at exhaustion (q(column)) were estimated for the removal of remazol reactive yellow and remazol reactive black by carbon adsorber. The results showed that column capacity calculated at 90% of column exhaustion was lower than carbon capacity obtained from equilibrium studies. This indicated that the capacity of activated carbon was not fully utilized in the fixed-bed adsorber. The bed-depth service time model (BDST) was applied for analysis of reactive yellow adsorption in the column. The adsorption capacity of reactive yellow calculated at 50% breakthrough point (No) was found to be 0.1 kg kg(-1) and this value is equivalent to about 14% of the available carbon capacity. The results of this study indicated the applicability of fixed-bed adsorber for removing remazol reactive yellow from solution. (C) 2008 Elsevier B.V. All rights reserved.

Adsorption of methylene blue onto activated carbon produced from steam activated bituminous coal: A study of equilibrium adsorption isotherm.

Chemical Engineering Journal, 124 (2006) 103.

Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon

The adsorption behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous solution onto activated carbon was investigated under various experimental conditions. The adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH 7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and Smith classification. The experimental adsorption data showed good correlation with the Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45, 0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes, respectively. Experimental data indicated that the adsorption capacity of activated carbon for the dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of dye increased with increase in the ionic strength of solution, this was attributed to aggregation of reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes onto activated carbon was an endothermic process. The adsorption enthalpy (?H) for C.I. Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol, respectively. The negative values of free energy (?G) determined for these systems indicated that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298-328 K). © 2007 Elsevier Ltd. All rights reserved.

Textile wastewater treatment using granular activated carbon adsorption in fixed beds

This work involved the treatment of industrial wastewater from a nylon carpet printing plant which currently receives no treatment and is discharged to sea. As nylon is particularly difficult to dye, acid dyes are required for successful coloration and cause major problems with the plant's effluent disposal in terms of color removal. Granular activated carbon Filtrasorb 400 was used to treat a ternary solution of acid dyes and the process plant effluent containing the dyes in a fixed-bed column system. Experimental data were correlated using the bed depth service time (BDST) model to previously published work by the authors for single dye adsorption. The results were expressed in terms of the BDST adsorption capacity, in milligrams of adsorbate per gram of adsorbent, and indicated that there was a 12-25% decrease iri adsorption capacity in the ternary system compared to the single component system; This reduction has been attributed to competitive adsorption occurring in the ternary component system. Dye adsorption from the process plant effluent showed an approximate 65% decrease in adsorption capacity compared to the ternary solution system. This has been attributed to interference caused by the other colorless textile effluent pollutants found in the process wastewater. A chemical oxygen demand analysis on these components indicated that the dyes accounted for only 14% of the total oxygen demand.

Prediction of bisolute dye adsorption isotherms on activated carbon

The removal of acid dyes, Tectilon Blue 4R, Tectilon Red 2B and Tectilon Orange 3G, from single solute, bisolute and trisolute solutions by adsorption on activated carbon (GAC F400) has been investigated in isotherm experiments. Results from these experiments were modelled using the Langmuir and Freundlich adsorption isotherm theories with the Langmuir model proving to be the more suitable. The Ideal Adsorbed Solution (IAS) model was coupled with the Langmuir isotherm to predict binary adsorption on the dyes. The application of the IAS theory accurately simulated the experimental data with an average deviation of approximately 3% between modelled and experimental data.

Influence of multiwall carbon nanotube functionality and loading on mechanical properties of PMMA/MWCNT bone cements

Poly (methyl methacrylate) (PMMA) bone cement—multi walled carbon nanotube (MWCNT) nanocomposites with weight loadings ranging from 0.1 to 1.0 wt% were prepared. The MWCNTs investigated were unfunctionalised, carboxyl and amine functionalised MWCNTs. Mechanical properties of the resultant nanocomposite cements were characterised as per international standards for acrylic resin cements. These mechanical properties were influenced by the type and wt% loading of MWCNT used. The morphology and degree of dispersion of the MWCNTs in the PMMA matrix at different length scales were examined using field emission scanning electron microscopy. Improvements in mechanical properties were attributed to the MWCNTs arresting/retarding crack propagation through the cement by providing a bridging effect and hindering crack propagation. MWCNTs agglomerations were evident within the cement microstructure, the degree of these agglomerations was dependent on the weight fraction and functionality of MWCNTs incorporated into the cement.

The distribution of late-Quaternary woody taxa in northern Eurasia: evidence from a new macrofossil database

We present a database of late-Quaternary plant macrofossil records for northern Eurasia (from 23 degrees to 180 degrees E and 46 degrees to 76 degrees N) comprising 281 localities, over 2300 samples and over 13,000 individual records. Samples are individually radiocarbon dated or are assigned ages via age models fitted to sequences of calibrated radiocarbon dates within a section. Tree species characteristic of modern northern forests (e.g. Picea, Larix, tree-Betula) are recorded at least intermittently from prior to the last glacial maximum (LGM), through the LGM and Lateglacial, to the Holocene, and some records locate trees close to the limits of the Scandinavian ice sheet, supporting the hypothesis that some taxa persisted in northern refugia during the last glacial cycle. Northern trees show differing spatio-temporal patterns across Siberia: deciduous trees were widespread in the Lateglacial, with individuals occurring across much of their contemporary ranges, while evergreen conifers expanded northwards to their range limits in the Holocene. (c) 2009 Elsevier Ltd. All rights reserved.

Carbon accumulation in peatlands of West Siberia over the last 2000 years

We use a network of cores from 77 peatland sites to determine controls on peat C content and peat C accumulation over the last 2000 years (since 2 ka) across Russia's West Siberian Lowland (WSL), the world's largest wetland region. Our results show a significant influence of fossil plant composition on peat C content, with peats dominated by Sphagnum having a lower C content. Radiocarbon-derived C accumulation since 2 ka at 23 sites is highly variable from site to site, but displays a significant N–S trend of decreasing accumulation at higher latitudes. Northern WSL peatlands show relatively small C accumulation of 7 to 35 kg C m-2 since 2 ka. In contrast, peatlands south of 60°N show larger accumulation of 42 to 88 kg C m-2. Carbon accumulation since 2 ka varies significantly with modern mean annual air temperature, with maximum C accumulation found between -1 and 0°C. Rates of apparent C accumulation since 2 ka show no significant relationship to long-term Holocene averages based on total C accumulation. A GIS-based extrapolation of our site data suggests that a substantial amount (~40%) of total WSL peat C has accumulated since 2 ka, with much of this accumulation south of 60°N. The large peatlands in the southern WSL may be an important component of the Eurasian terrestrial C sink, and future warming could result in a shift northward in long-term WSL C sequestration.

FTIR analysis of water in supercritical carbon dioxide microemulsions using monofunctional perfluoropolyether surfactants

We describe perfluoropolyether (PFPE) surfactants which are capable of stabilising the water/CO2 interface and present FTIR spectroscopic evidence for the formation of water in supercritical carbon dioxide microemulsions. A wide variety of single chain surfactants of differing chain lengths but similar structure has been screened and the effect of the surfactant chain length on the water uptake was studied. The ammonium carboxylate of the PFPE surfactant Krytox FSL(TM) with an average molecular weight of 2500 g mol(-1) was demonstrated to be the surfactant capable of dissolving the most water out of all the tested surfactants and hence to have the optimum chain length. (C) 2002 Elsevier Science B.V. All rights reserved.