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.

The effect of feedstock cost on biofuel cost as exemplified by biomethane production from grass silage.

Abstract: The potential variance in feedstock costs can have signifi cant implications for the cost of a biofuel and the fi nancial viability of a biofuel facility. This paper employs the Grange Feed Costing Model to assess the cost of on-farm biomethane production using grass silages produced under a range of management scenarios. These costs were compared with the cost of wheat grain and sugarbeet roots for ethanol production at an industrial scale. Of the three feedstocks examined, grass silage represents the cheapest feedstock per GJ of biofuel produced. At a production cost of €27/tonne (t) feedstock (or €150/t volatile solids (VS)), the feedstock production cost of grass silage per gigajoule (GJ) of biofuel (€12.27) is lower than that of sugarbeet (€16.82) and wheat grain (€18.61). Grass biomethane is also the cheapest biofuel when grass silage is costed at the bottom quartile purchase price of silage of €19/t (€93/t VS). However, when considering the production costs (full-costing) of the three feedstocks, the total cost of grass biomethane (€32.37/GJ of biofuel; intensive 2-cut system) from a small on-farm facility ranks between that of sugarbeet (€29.62) and wheat grain ethanol (€34.31) produced in large industrial facilities. The feedstock costs for the above three biofuels represent 0.38, 0.57, and 0.54 of the total biofuel cost. The importance of feedstock cost on biofuel cost is further highlighted by the 0.43 increase in the cost of biomethane when grass silage is priced at the top quartile (€46/t or €232/t VS) compared to the bottom quartile purchase price.

Modeling study of woody biomass:Interactions of cellulose, hemicellulose, and lignin

Lignocellulosic biomass pretreatment and the subsequent thermal conversion processes to produce solid, liquid, and gas biofuels are attractive solutions for today's energy challenges. The structural study of the main components in biomass and their macromolecular complexes is an active and ongoing research topic worldwide. The interactions among the three main components, cellulose, hemicellulose, and lignin, are studied in this paper using electronic structure methods, and the study includes examining the hydrogen bond network of cellulose-hemicellulose systems and the covalent bond linkages of hemicellulose-lignin systems. Several methods (semiempirical, Hartree-Fock, and density functional theory) using different basis sets were evaluated. It was shown that theoretical calculations can be used to simulate small model structures representing wood components. By comparing calculation results with experimental data, it was concluded that B3LYP/6-31G is the most suitable basis set to describe the hydrogen bond system and B3LYP/6-31G(d,p) is the most suitable basis set to describe the covalent system of woody biomass. The choice of unit model has a much larger effect on hydrogen bonding within cellulose-hemicellulose system, whereas the model choice has a minimal effect on the covalent linkage in the hemicellulose-lignin system. © 2011 American Chemical Society.

An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasifi- cation, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day1 of OME3, OME4, and OME5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno- economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.

The vegetation and climate history of the last glacial cycle in a new pollen record from Lake Fimon (southern Alpine foreland, N-Italy)

The sediments of Like Fimon N Italy contain the first continuous archive of the Late Pleistocene environmental and climate history of the southern Alpine foreland We present here the detailed palynological record of the interval between Termination II and the List Glacial Maximum The age-depth model is obtained by radiocarbon dating in the uppermost part of the record Downward we con elated major forest expansion and contraction events to isotopic events in the Greenland Ice core records via a stepping-stone approach involving intermediate correlation to isotopic events dated by TIMS U/Th in Alpine and Apennine stalagmites and to pollen records from mime cores of the Iberian margin Modelled ages obtained by Bayesian analysis of deposition are thoroughly consistent with actual ages with maximum offset of +/- 1700 years Sharp expansion of broad-leaved temperate forest and of sudden water table rise mark the onset of the Last Interglacial after a treeless steppe phase at the end of penultimate glaciation This event is actually a two-step process which matches the two step rise observed in the isotopic record of the nearby Antro del Corchia stalagmite respectively dated to 132 5 +/- 2 5 and 129 +/- 1 5 ka At the interglacial decline mixed oak forests were replaced by oceanic mixed forests the latter persisting further for 7 ka till the end of the Eemian succession Warm-temperate woody species are still abundant at the Eemian end corroborating a steep gradient between central Europe and the Alpine divide at the inception of the last glacial After a stadial phase marked by moderate forest decline a new expansion of warm broad leaved forests interrupted by minor events and followed by mixed oceanic forests can be identified with the north-alpine Saint Germain I The spread of beech during the oceanic phase is a valuable circumalpine marker The subsequent stadial-interstadial succession lacking the telocratic oceanic phase is also consistent with the evidence at the north alpine foreland The Middle Wurmian (full glacial) is marked by persistence of mixed forests dominated by conifers but with significant lime and other broad leaved species A major Arboreal Pollen decrease is observed at modelled age of 38 7 +/- 0 5 ka (larch expansion and last occurrence of lime) which his been related to Heinrich Event 4 The evidence of afforestation persisting south of the Alps throughout most of MIS 3 contrasts with a boreal and continental landscape known for the northern alpine foreland pointing to a sharp rainfall boundary at the Alpine divide and to southern air circulation This is in agreement with the Alpine paleoglaciological record and is supported by the pressure and rainfall patterns designed by mesoscale paleoclimate simulations Strenghtening the continental high pressure during the full glacial triggered cyclogenesis in the middle latitude eastern Europe and orographic rainfall in the eastern Alps and the Balkanic mountains thus allowing forests development at current sea level altitudes (C) 2010 Elsevier Ltd All rights reserved

Preparation and characterisation of cellulose nanofibres

Two different procedures were compared for the preparation of cellulose nanofibres from flax and microcrystalline cellulose (MCC). The first involved a combination of high energy ball milling, acid hydrolysis and ultrasound, whilst the second employed a high pressure homogenisation technique, with and without various pre-treatments of the fibrous feedstock. The geometry and microstructure of the cellulose nanofibres were observed by SEM and TEM and their particle size measured using image analysis and dynamic light scattering. Aspect ratios of nanofibres made by microfluidisation were orders of magnitude greater than those achieved by acid hydrolysis. FTIR, XRD and TGA were used to characterise changes to chemical functionality, cellulose crystallinity and thermal stability resulting from the approaches used for preparing the cellulose nanofibres. Hydrolysis using sulphuric acid gave rise to esterification of the cellulose nanofibres, a decrease in crystallinity with MCC, but an increase with flax, together with an overall reduction in thermal stability. Increased shear history of flax subjected to multiple passes through the microfluidiser, raised both cellulose nanofibril crystallinity and thermal stability, the latter being strongly influenced by acid, alkaline and, most markedly, silane pretreatment.

Controlling Assembly of Mixed Thiol Monolayers on Silver Nanoparticles to Tune Their Surface Properties

Modifying the surfaces of metal nanoparticles with self-assembled monolayers of functionalized thiols provides a simple and direct method to alter their surface properties. Mixed self-assembled monolayers can extend this approach since, in principle, the surfaces can be tuned by altering the proportion of each modifier that is adsorbed. However, this works best if the composition and microstructure of the monolayers can be controlled. Here, we have modified preprepared silver colloids with binary mixtures of thiols at varying concentrations and modifier ratios. Surface-enhanced Raman spectroscopy was then used to determine the effect of altering these parameters on the composition of the resulting mixed monolayers. The data could be explained using a new model based on a modified competitive Langmuir approach. It was found that the composition of the mixed monolayer only reflected the ratio of modifiers in the feedstock when the total amount of modifier was sufficient for approximately one monolayer coverage. At higher modifier concentrations the thermodynamically favored modifier dominated, but working at near monolayer concentrations allowed the surface composition to be controlled by changing the ratios of modifiers. Finally, a positively charged porphyrin probe molecule was used to investigate the microstructure of the mixed monolayers, i.e., homogeneous versus domains. In this case the modifier domains were found to be <2 nm.

A study of the use of the trimesium salt of glyphosate to desiccate and ret flax and linseed (Linum usitatissimum) and of its effects on the yield of straw, seed and fibre

A replicated field plot experiment was carried out in Northern Ireland in 1996 with flax, cv Ariane, and linseed, cv Flanders, each grown at seed rates of 500, 1000 and 1500 seeds/m(2), in which a comparison was made between netting of the standing crop, following desiccation by the trimesium salt of glyphosate (Touchdown, Zeneca Ltd.), and water or dew retting of the pulled crop. Application at 4 litres/ha on 9 August, 33 days after the mid-point of flowering (MPF), achieved both desiccation and partial retting of the crop within 14 days. Over 16 % clean long fibre was extracted by scutching the stand-netted flax straw, yielding 800 kg/ha fibre, while water retting achieved 20 extraction and 980 kg/ha yield and dew netting 8.5 % and 420 kg/ha respectively. The dew retting was uneven, resulting in high losses during fibre extraction, while water retting for 7 days at 25 degreesC did not achieve complete retting resulting in a high content of woody fragments in the fibre. Fibre yields increased by almost 50 % with the high v. low seed rate. Linseed was less well retted than flax and contained higher levels of impurity in the extracted long fibre which, after retting, yielded 120 to 310 kg/ha at extraction rates of 2.9 % to 7.5 %.

In a second experiment in 1998 flax cvs. Viola and Evelyn were treated with the timesium salt of glyphosate at rates of 2, 4 or 6 litres/ha 10, 20, 30 or 40 days after MPF on 5 July. Viola desiccated satisfactorily at all spray dates with 4 and 6 litres/ha glyphosate. The 20-day treatment desiccated more slowly than the 30-day and the 2 litres/ha rate did not achieve complete desiccation, but the trimesium salt of glyphosate achieved better desiccation at this timing than that found in earlier studies with the original form of glyphosate. Evelyn desiccated more slowly and less evenly than Viola particularly at the 20-day and 40-day timings. Spraying at MPF + 10 days interrupted early development of the seed and fibre significantly reducing yields. Due to slower desiccation the 20-day timing was no better than the 30-day, which was well retted by harvest 44 days after spraying, and gave the highest yield of clean long fibre. The spraying 40 days after MPF was considered too late in the season to be of practical use. It was concluded that retting of standing flax following desiccation with the trimesium salt of glyphosate was more effective than with the earlier formulation and that resting of the standing crop could achieve equivalent or better retting with similar fibre yields to traditional retting methods. The optimum spray timing was found to be about 30 days after MPF with 4 or 6 litres/ha, the lower rate being adequate for glyphosate responsive varieties such as Viola.

Determining the regional potential for a grass biomethane industry

Grass biogas/biomethane has been put forward as a renewable energy solution and it has been shown to perform well in terms of energy balance, greenhouse gas emissions and policy constraints. Biofuel and energy crop solutions are country-specific and grass biomethane has strong potential in countries with temperate climates and a high proportion of grassland, such as Ireland. For a grass biomethane industry to develop in a country, suitable regions (i.e. those with the highest potential) must be identified. In this paper, factors specifically related to the assessment of the potential of a grass biogas/biomethane industry are identified and analysed. The potential for grass biogas and grass biomethane is determined on a county-by-county basis using multi-criteria decision analysis. Values are assigned to each county and ratings and weightings applied to determine the overall county potential. The potential for grass biomethane with co-digestion of slaughter waste (belly grass) is also determined. The county with the highest potential (Limerick) is analysed in detail and is shown to have ready potential for production of gaseous biofuel to meet either 50% of the vehicle fleet or 130% of the domestic natural gas demand, through 25 facilities at a scale of ca. 30ktyr of feedstock. The assessment factors developed in this paper can be used in other resource studies into grass biomethane or other energy crops. © 2010 Elsevier Ltd.

Can grass biomethane be an economically viable biofuel for the farmer and the consumer?

Farm incomes in Ireland are in decline and many farmers would operate at a loss in the absence of subsidies. Agriculture is responsible for 27% of Ireland's greenhouse gas emissions and is the largest contributing sector. Penetration of renewable energy in the heat and transport sectors is falling short of targets, and there is no clear plan for achieving them. The anaerobic digestion of grass to produce biogas or biomethane is put forward as a multifaceted solution, which could help meet energy and emissions targets, reduce dependence on imported energy, and provide additional farm income. This paper addresses the economic viability of such a system. Grass biogas/biomethane fares poorly under the current combined heat and power tariff structure, which is geared toward feedstock that attracts a gate fee. Tariff structures similar to those used in other countries are necessary for the industry to develop. Equally, regulation should be implemented to allow injection of biomethane into the gas grid in Ireland. Blends of natural gas and biomethane can be sold, offering a cost-competitive green fuel. Sale as a renewable transport fuel could allow profitability for the farmer and savings for the consumer, but suffers due to the lack of a market. Under current conditions, the most economically viable outlet for grass biomethane is sale as a renewable heating fuel. The key to competitiveness is the existing natural gas infrastructure that enables distribution of grass biomethane, and the renewable energy targets that allow renewable fuels to compete against each other. © 2010 Society of Chemical Industry and John Wiley & Sons, Ltd.

Hydrolysis characteristics and kinetics of waste hay biomass as a potential energy crop for fermentable sugars production using autoclave parr reactor system

The use of the organic fraction of municipal solid waste crops has received considerable attention as a sustainable feedstock that can replace fossil fuels for the production of renewable energy. Therefore, municipal bin-waste in the form of hay was investigated as a potential energy crop for fermentable sugars production. Hydrolysis of hay by dilute phosphoric acid was carried out in autoclave parr reactor, where reactor temperature (135-200 degrees c) and acid concentration (2.5-10% (w/w)) were examined. Analysis of the decomposition rate of hemicellulosic biomass was undertaken using HPLC of the reaction products. Xylose production reached a maximum value of 13.5 g/100 g dry mass corresponding to a yield of 67% at the best identified conditions of 2.5 wt% H3PO4, 175 degrees C, 10 min reaction time, and at 5 wt% H3PO4, 150 degrees C, and 5 min reaction time. For glucose, an average yield of 25% was obtained at 5 wt% H3PO4, 175 degrees C and 30 min. Glucose degradation to HMF was achieved at 10 wt% H3PO4 and 200 degrees C. The maximum yield for produced arabinose was an average of 3 g/100 g dry. mass corresponding to 100% of the total possible arabinose. The kinetic study of the acid hydrolysis was also carried out using the Saeman and the Two-fraction models. It was found for both models that the kinetic constants (k) depend on the acid concentration and temperature. For xylose and arabinose it was found that the rate of formation was more favoured than the rate of degradation. By contrast, for glucose it was found that glucose degradation was occurring faster than glucose formation. It can be concluded that dilute phosphoric acid hydrolysis of hay crop is feasible for the production of fermentable sugars which are essential for bioethanol synthesis. 

Dilute phosphoric acid-catalysed hydrolysis of municipal bio-waste wood shavings using autoclave parr reactor system

The visibility of using municipal bio-waste, wood shavings, as a potential feedstock for ethanol production was investigated. Dilute acid hydrolysis of wood shavings with H3PO4 was undertaken in autoclave parr reactor. A combined severity factor (CSF) was used to integrate the effects of hydrolysis times, temperature and acid concentration into a single variable. Xylose concentration reached a maximum value of 17 g/100 g dry mass corresponding to a yield of 100% at the best identified conditions of 2.5 wt.% H3PO4, 175 degrees C and 10 min reaction time corresponding to a CSF of 1.9. However, for glucose, an average yield of 30% was obtained at 5 wt.% H3PO4, 200 degrees C and 10 min. Xylose production increased with increasing temperature and acid concentration, but its transformation to the degradation product furfural was also catalysed by those factors. The maximum furfural formed was 3 g/100 g dry mass, corresponding to the 24% yield. (C) 2011 Elsevier Ltd. All rights reserved.

TAP studies on 2% Ag/gamma-Al2O3 catalyst for selective reduction of oxygen in a H-2-rich ethylene feed

Catalysts currently employed for the polymerization of ethylene have previously been found to deactivate in the presence of oxygen. It is, therefore, important that oxygen is removed from the ethylene feedstock prior to the polymerization. The Ag/gamma-Al2O3 catalyst exhibits excellent activity and selectivity toward oxygen reduction with hydrogen in the presence of ethylene. TAP vacuum pulse experiments have been utilised to understand the catalytic behaviour of the Ag/gamma-Al2O3 catalyst. TAP multi-pulse experiments have determined the types of active sites that are found on the Ag/gamma-Al2O3 catalyst, and the intrinsic activity of these sites. The lifetime of the reactive adsorbed oxygen intermediate has also been determined through TAP consecutive pulse experiments. Multi-pulse and consecutive pulse data have been combined with ethylene adsorption/desorption rate constants to provide an overview of the Ag/gamma-Al2O3 catalyst system.

Fermentable sugars recovery from lignocellulosic waste-newspaper by catalytic hydrolysis

The urgent need for alternative renewable energies to supplement petroleum-based fuels and the reduction of landfill sites for disposal of solid wastes makes it increasingly attractive to produce inexpensive biofuels from the organic fraction of the municipal solid waste. Therefore, municipal waste in the form of newspaper was investigated as a potential feedstock for fermentable sugars production. Hydrolysis of newspaper by dilute phosphoric acid was carried out in autoclave Parr reactor, where reactor temperature and acid concentration were examined. Xylose concentration reached a maximum value of 14 g/100 g dry mass corresponding to a yield of 94% at the best identified conditions of 2.5 wt% HPO, 135°C, 120 min reaction time, and at 2.5 wt% HPO, 150°C, and 60 min reaction time. For glucose, an average yield of 26% was obtained at 2.5 wt% HPO, 200°C, and 30 min. Furfural and 5-hydroxymethylfurfural (HMF) formation was clearly affected by reaction temperature, where the higher the temperature the higher the formation rate. The maximum furfural formed was an average of 3 g/100 g dry mass, corresponding to a yield of 28%. The kinetic study of the acid hydrolysis was also carried out using the Saeman and the two-fraction models. It was found for both models that the kinetic constants (K) depend on the acid concentration and temperature. The degradation of HMF to levulinic acid is faster than the degradation of furfural to formic acid. Also, the degradation rate is higher than the formation rate for both inhibitors when degradation is observed.

Determining the response of African biota to climate change: using the past to model the future

Prediction of biotic responses to future climate change in tropical Africa tends to be based on two modelling approaches: bioclimatic species envelope models and dynamic vegetation models. Another complementary but underused approach is to examine biotic responses to similar climatic changes in the past as evidenced in fossil and historical records. This paper reviews these records and highlights the information that they provide in terms of understanding the local- and regional-scale responses of African vegetation to future climate change. A key point that emerges is that a move to warmer and wetter conditions in the past resulted in a large increase in biomass and a range distribution of woody plants up to 400–500 km north of its present location, the so-called greening of the Sahara. By contrast, a transition to warmer and drier conditions resulted in a reduction in woody vegetation in many regions and an increase in grass/savanna-dominated landscapes. The rapid rate of climate warming coming into the current interglacial resulted in a dramatic increase in community turnover, but there is little evidence for widespread extinctions. However, huge variation in biotic response in both space and time is apparent with, in some cases, totally different responses to the same climatic driver. This highlights the importance of local features such as soils, topography and also internal biotic factors in determining responses and resilience of the African biota to climate change, information that is difficult to obtain from modelling but is abundant in palaeoecological records.