Market of biomass fuels in Finland : IEA Bioenergy Task 40 and EUBIONET III - Country report of Finland 2009

This study considered the current situation of solid and liquid biomass fuels in Finland. The fact that industry consumes more than half of the total primary energy, widely applied combined heat and power production and a high share of solid biomass fuels in the total energy consumption are specific to the Finnish energy system. Wood is the most important source of bioenergy in Finland, representing 20% of the total energy consumption in 2007. Almost 80% of the woodbased energy is recovered from industrial by-products and residues. As a member of the European Union, Finland has committed itself to the Union’s climate and energy targets, such as reducing its overall emissions of green house gases to at least 20% below 1990 levels by 2020, and increasing the share of renewable energy in the gross final consumption. The renewable energy target approved for Finland is 38%. The present National Climate and Energy Strategy was introduced in November 2008. The strategy covers climate and energy policy measures up to 2020, and in brief thereafter, up to 2050. In recent years, the actual emissions have exceeded the Kyoto commitment and the trend of emissions is on the increase. In 2007, the share of renewable energy in the gross final energy consumption was approximately 25% (360 PJ). Without new energy policy measures, the final consumption of renewable energy would increase to 380 PJ, which would be approximately only 31% of the final energy consumption. In addition, green house gas emissions would exceed the 1990 levels by 20%. Meeting the targets will need the adoption of more active energy policy measures in coming years. The international trade of biomass fuels has a substantial importance for the utilisation of bioenergy in Finland. In 2007, the total international trading of solid and liquid biomass fuels was approximately 77 PJ, of which import was 62 PJ. Most of the import is indirect and takes place within the forest industry’s raw wood imports. In 2007, as much as 21% of wood energy was based on foreign-origin wood. Wood pellets and tall oil form the majority of export streams of biomass fuels. The indirect import of wood fuels peaked in 2006 to 61 PJ. The foreseeable decline in raw wood import to Finland will decrease the indirect import of wood fuels. In 2004– 2007, the direct trade of solid and liquid biomass fuels has been on a moderate growth path. In 2007, the import of palm oil and export of bio-diesel emerged, as a large, 170 000 t/yr biodiesel plant came into operation in Porvoo.

Free PAPP-A: a Novel Marker in Acute Coronary Syndrome Patients

In recent years, one important objective of cardiovascular research has been to find new markers that would improve the risk stratification and diagnosis of patients presenting with symptoms of acute coronary syndrome (ACS). Pregnancy-associated plasma protein A (PAPP-A) is a large metalloproteinase involved in insulin-like growth factor signalling. It is expressed in various tissues and seems to be involved in many physiological and pathological processes, such as folliculogenesis, bone formation, wound healing, pregnancy and atherosclerosis. The aim of this thesis was to investigate PAPP-A in ACS patients. Circulating concentrations of PAPP-A had been previously shown to be elevated in ACS. In this study it was revealed that the form of PAPP-A causing this elevation was the free noncomplexed PAPP-A. Thus, the form of PAPP-A in the circulation of ACS patients differed from the complexed PAPP-A form abundantly present in the circulation during pregnancy. A point-of-care method based on time-resolved immunofluorometric assays was developed, which enabled the rapid detection of free PAPP-A. The method was found to perform well with serum and heparin plasma samples as well as with heparinized whole blood samples. With this method the concentrations of free PAPP-A in healthy individuals were shown to be negligible. When the clinical performance of the method was evaluated with serum samples from ACS patients, it was shown that the free PAPP-A concentration in the admission sample was an independent predictor of myocardial infarction and death. Moreover, as a prognostic marker, free PAPP-A was revealed to be superior to total PAPPA, i.e. the combination of free and complexed PAPP-A, which has been measured by the other groups in this field. As heparin products are widely used as medication in ACS patients, the effect of heparin products on free PAPP-A molecule and circulating concentrations were also investigated in this study. It was shown that intravenous administration of low molecular weight or unfractionated heparin elicits a rapid release of free PAPP-A into the circulation in haemodialysis patients and patients undergoing angiography. Moreover, the interaction between PAPP-A and heparin was confirmed in gel filtration studies. Importantly, the patients included in the clinical evaluation of the free PAPP-A detection method developed had not received any heparin product medication before the admission sample and thus the results were not affected by the heparin effect. In conclusion, free PAPP-A was identified as a novel marker associated with ACS. The point-of-care methods developed enable rapid detection of this molecule which predicts adverse outcome when measured in the admission sample of ACS patients. However, the effect revealed of heparin products on circulating PAPP-A concentrations should be acknowledged when further studies are conducted related to free or total PAPP-A in ACS.

Forest Biomass Resources and Technological Prospects for the Production of Second-generation Biofuels in Finland by 2020

Introduction of second-generation biofuels is an essential factor for meeting the EU’s 2020 targets for renewable energy in the transport sector and enabling the more ambitious targets for 2030. Finland’s forest industry is strongly involved in the development and commercialising of second-generation biofuel production technologies. The goal of this paper is to provide a quantified insight into Finnish prospects for reaching the 2020 national renewable energy targets and concurrently becoming a large-scale producer of forest biomass based second-generation biofuels feeding the increasing demand in European markets. The focus of the paper is on assessing the potential for utilising forest biomass for liquid biofuels up to 2020. In addition, technological issues related to the production of second-generation biofuels were reviewed. Finland has good opportunities to realise a scenario to meet 2020 renewable energy targets and for large-scale production of wood based biofuels. In 2020, biofuel production from domestic forest biomass in Finland may reach nearly a million ton (40 PJ). With the existing biofuel production capacity (20 PJ/yr) and national biofuel consumption target (25 PJ) taken into account, the potential net export of biofuels from Finland in 2020 would be 35 PJ, corresponding to 2–3% of European demand. Commercialisation of second-generation biofuel production technologies, high utilisation of the sustainable harvesting potential of Finnish forest biomass, and allocation of a significant proportion of the pulpwood harvesting potential for energy purposes are prerequisites for this scenario. Large-scale import of raw biomass would enable remarkably greater biofuel production than is described in this paper.

Developing markets of energy biomass – local and global perspectives

The thesis explores global and national-level issues related to the development of markets for biomass for energy. The thesis consists of five separate papers and provides insights on selected issues. The aim of Paper I was to identify methodological and statistical challenges in assessing international solid and liquid biofuels trade and provide an overview of the Finnish situation with respect to the status of international solid and liquid biofuels trade. We found that, for the Finnish case, it is possible to qualify direct and indirect trade volumes of biofuels. The study showed that indirect trade of biofuels has a highly significant role in Finland and may be a significant sector also in global biofuels trade. The purpose of Paper II was to provide a quantified insight into Finnish prospects for meeting the national 2020 renewable energy targets and concurrently becoming a largescale producer of forest-biomass-based second-generation biofuels for feeding increasing demand in European markets. We found that Finland has good opportunities to realise a scenario to meet 2020 renewable energy targets and for large-scale production of wood-based biofuels. The potential net export of transport biofuels from Finland in 2020 would correspond to 2–3% of European demand. Paper III summarises the global status of international solid and liquid biofuels trade as illuminated by several separate sources. International trade of biofuels was estimated at nearly 1 EJ for 2006. Indirect trade of biofuels through trading of industrial roundwood and material by-products comprises the largest proportion of the trading, with a share of about two thirds. The purpose of Paper IV was to outline a comprehensive picture of the coverage of various certification schemes and sustainability principles relating to the entire value-added chain of biomass and bioenergy. Regardless of the intensive work that has been done in the field of sustainability schemes and principles concerning use of biomass for energy, weaknesses still exist. The objective of Paper V was to clarify the alternative scenarios for the international biomass market until 2020 and identify the underlying steps needed toward a wellfunctioning and sustainable market for biomass for energy purposes. An overall conclusion drawn from this analysis concerns the enormous opportunities related to the utilisation of biomass for energy in the coming decades.

Combustion properties of biomass residues rich in phosphorus

Tillgången på traditionella biobränslen är begränsad och därför behöver man ta fram nya, tidigare outnyttjade biobränslen för att möta de uppställda CO2 emissionsmålen av EU och det ständigt ökande energibehovet. Under de senare åren har intresset riktats mot termisk energiutvinning ur olika restfraktioner och avfall. Vid produktion av fordonsbränsle ur biomassa är den fasta restprodukten ofta den största procesströmmen i produktionsanläggningen. En riktig hantering av restprodukterna skulle göra produktionen mera lönsam och mer ekologiskt hållbar. Ett alternativ är att genom förbränning producera elektricitet och/eller värme eftersom dessa restprodukter anses som CO2-neutrala. Målsättningen med den här avhandlingen var att studera förbränningsegenskaperna hos några fasta restprodukter som uppstår vid framställning av förnybara fordonsbränslen. De fyra undersökta materialen är rapskaka, palmkärnskaka, torkad drank och stabiliserat rötslam. I studien används ett stort urval av undersökningsmetoder, från laboratorieskala till fullskalig förbränning, för att identifiera de huvudsakliga utmaningarna förknippade med förbränning av restprodukterna i pannor med fluidiserad bäddteknik. Med hjälp av detaljerad bränslekarakterisering kunde restprodukterna konstateras vara en värdefull källa för värme- och elproduktion. Den kemiska sammansättningen av restprodukterna varierar stort jämfört med mera traditionellt använda biobränslen. En gemensam faktor för alla de studerade restprodukterna är en hög fosforhalt. På grund av de låga fosforkoncentrationerna i de traditionella biobränslena har grundämnet hittills inte ansetts spela någon större roll i askkemin. Experimenten visade nu att fosfor inte mera kan försummas då man studerar kemin i förbränningsprocesser, då allt flera fosforrika bränslen tränger in på energimarknaden.

Biomass fractionation

The objective of this master's thesis was to develop a process to increase the value of residual fungal biomass as an animal feed. The increase in value is achieved by enriching the protein content in the biomass and potentially isolating other valuable fractions for productisation. In the literature part of this thesis the composition of fungal biomass and fungal cell wall and the factors affecting them during cultivation are presented. The possible processing options are also presented and evaluated. The soy protein and single cell protein product manufacturing processes are used as examples due to the lack of fungal biomass fractionation processes found in published literature. The second part of this thesis was performed by making laboratory experiments on the developed process, which consisted of acid hydrolysis with subsequent ethanol extraction. Chitin was precipitated from the acid hydrolysate filtrate. The experiments were conducted with three different hydrolysis temperatures and three different acid concentrations. The optimal hydrolysis conditions were 60 °C with 10 %-vol acid concentration. Optimal conditions in hydrolysis resulted in 30 % increase in protein content in the final biomass. The conceptual process was modelled to scale of 10 000 t/a biomass feed. The mass and energy balances were based on the laboratory experiments. Economic calculations were performed to determine the maximal capital expense while achieving 10 % internal rate of return for the investment. For the basic case the capital expense threshold was 25.8 M€. Four optional cases and parameter sensitivity analysis were performed to determine the effects of changes in the process. The chitin sales had the greatest impact of the individual parameters.

Catalysis by gold for biomass transformations

The development of new technologies to supplement fossil resources has led to a growing interest in the utilization of alternative routes. Biomass is a rich renewable feedstock for producing fine chemicals, polymers, and a variety of commodities replacing petroleumderived chemicals. Transformation of biomass into diverse valuable chemicals is the key concept of a biorefinery. Catalytic conversion of biomass, which reduces the use of toxic chemicals is one of the important approaches to improve the profitability of biorefineries. Utilization of gold catalysts allows conducting reactions under environmentally-friendly conditions, with a high catalytic activity and selectivity. Gold-catalyzed valorization of several biomass-derived compounds as an alternative approach to the existing technologies was studied in this work. Isomerization of linoleic acid via double bond migration towards biologically active conjugated linoleic acid isomers (CLA) was investigated. The activity and selectivity of various gold catalysts towards cis-9,trans-11-CLA and trans-10,cis-12-CLA were investigated in a semi-batch reactor, showing that the yield of the desired products varied, depending on the catalyst support. The structure sensitivity in the selective oxidation of arabinose was demonstrated using a series of gold catalysts with different Au cluster sizes in a shaker reactor operating in a semibatch mode. The gas-phase selective oxidation of ethanol was studied and the influence of the catalyst support on the catalytic performance was investigated. The selective oxidation of the lignan hydroxymatairesinol (HMR), extracted from the Norway spruce (Picea abies) knots, to the lignan oxomatairesinol (oxoMAT) was extensively investigated. The influence of the reaction conditions and catalyst properties on the yield of oxoMAT was evaluated. In particular, the structure sensitivity of the reaction was demonstrated. The catalyst deactivation and regeneration procedures were studied. The reaction kinetics and mechanism were advanced.

A platform for anti-biofilm assays combining viability, biomass and matrix quantifications in susceptibility assessments of antimicrobials against Staphylococcus aureus biofilms

Bacteria can exist as planktonic, the lifestyle in which single cells exist in suspension, and as biofilms, which are surface-attached bacterial communities embedded in a selfproduced matrix. Most of the antibiotics and the methods for antimicrobial work have been developed for planktonic bacteria. However, the majority of the bacteria in natural habitats live as biofilms. Biofilms develop dauntingly fast high resistance towards conventional antibacterial treatments and thus, there is a great need to meet the demands of effective anti-biofilm therapy. In this thesis project it was attempted to fill the void of anti-biofilm screening methods by developing a platform of assays that evaluate the effect that screened compounds have on the total biomass, viability and the extracellular polysaccharide (EPS) layer of the biofilms. Additionally, a new method for studying biofilms and their interactions with compounds in a continuous flow system was developed using capillary electrochromatography (CEC). The screening platform was utilized with a screening campaign using a small library of cinchona alkaloids. The assays were optimized to be statistically robust enough for screening. The first assay, based on crystal violet staining, measures total biofilm biomass, and it was automated using a liquid handling workstation to decrease the manual workload and signal variation. The second assay, based on resazurin staining, measures viability of the biofilm, and it was thoroughly optimized for the strain used, but was then a very simple and fast method to be used for primary screening. The fluorescent resazurin probe is not toxic to the biofilms. In fact, it was also shown in this project that staining the biofilms with resazurin prior to staining with crystal violet had no effect on the latter and they can be used in sequence on the same screening plate. This sequential addition step was indeed a major improvement on the use of reagents and consumables and also shortened the work time. As a third assay in the platform a wheat germ agglutinin based assay was added to evaluate the effect a compound has on the EPS layer. Using this assay it was found that even if compounds might have clear effect on both biomass and viability, the EPS layer can be left untouched or even be increased. This is a clear implication of the importance of using several assays to be able to find “true hits” in a screening setting. In the pilot study of screening for antimicrobial and anti-biofilm effects using a cinchona alkaloid library, one compound was found to have antimicrobial effect against planktonic bacteria and prevent biofilm formation at low micromolar concentration. To eradicate biofilms, a higher concentration was needed. It was also shown that the chemical space occupied by the active compound was slightly different than the rest of the cinchona alkaloids as well as the rest of the compounds used for validatory screening during the optimization processes of the separate assays.

Reflexive Space. A Constructionist Model of the Russian Reflexive Marker

This study examines the structure of the Russian Reflexive Marker ( ся/-сь) and offers a usage-based model building on Construction Grammar and a probabilistic view of linguistic structure. Traditionally, reflexive verbs are accounted for relative to non-reflexive verbs. These accounts assume that linguistic structures emerge as pairs. Furthermore, these accounts assume directionality where the semantics and structure of a reflexive verb can be derived from the non-reflexive verb. However, this directionality does not necessarily hold diachronically. Additionally, the semantics and the patterns associated with a particular reflexive verb are not always shared with the non-reflexive verb. Thus, a model is proposed that can accommodate the traditional pairs as well as for the possible deviations without postulating different systems. A random sample of 2000 instances marked with the Reflexive Marker was extracted from the Russian National Corpus and the sample used in this study contains 819 unique reflexive verbs. This study moves away from the traditional pair account and introduces the concept of Neighbor Verb. A neighbor verb exists for a reflexive verb if they share the same phonological form excluding the Reflexive Marker. It is claimed here that the Reflexive Marker constitutes a system in Russian and the relation between the reflexive and neighbor verbs constitutes a cross-paradigmatic relation. Furthermore, the relation between the reflexive and the neighbor verb is argued to be of symbolic connectivity rather than directionality. Effectively, the relation holding between particular instantiations can vary. The theoretical basis of the present study builds on this assumption. Several new variables are examined in order to systematically model variability of this symbolic connectivity, specifically the degree and strength of connectivity between items. In usage-based models, the lexicon does not constitute an unstructured list of items. Instead, items are assumed to be interconnected in a network. This interconnectedness is defined as Neighborhood in this study. Additionally, each verb carves its own niche within the Neighborhood and this interconnectedness is modeled through rhyme verbs constituting the degree of connectivity of a particular verb in the lexicon. The second component of the degree of connectivity concerns the status of a particular verb relative to its rhyme verbs. The connectivity within the neighborhood of a particular verb varies and this variability is quantified by using the Levenshtein distance. The second property of the lexical network is the strength of connectivity between items. Frequency of use has been one of the primary variables in functional linguistics used to probe this. In addition, a new variable called Constructional Entropy is introduced in this study building on information theory. It is a quantification of the amount of information carried by a particular reflexive verb in one or more argument constructions. The results of the lexical connectivity indicate that the reflexive verbs have statistically greater neighborhood distances than the neighbor verbs. This distributional property can be used to motivate the traditional observation that the reflexive verbs tend to have idiosyncratic properties. A set of argument constructions, generalizations over usage patterns, are proposed for the reflexive verbs in this study. In addition to the variables associated with the lexical connectivity, a number of variables proposed in the literature are explored and used as predictors in the model. The second part of this study introduces the use of a machine learning algorithm called Random Forests. The performance of the model indicates that it is capable, up to a degree, of disambiguating the proposed argument construction types of the Russian Reflexive Marker. Additionally, a global ranking of the predictors used in the model is offered. Finally, most construction grammars assume that argument construction form a network structure. A new method is proposed that establishes generalization over the argument constructions referred to as Linking Construction. In sum, this study explores the structural properties of the Russian Reflexive Marker and a new model is set forth that can accommodate both the traditional pairs and potential deviations from it in a principled manner.

PV-1: Leukocyte trafficking molecule and vascular marker

The distinction between lymphatic vessels and blood vessels is a crucial factor in many studies in immunology, vascular biology and cancer biology. They both share several characteristics and perform related, though different functions. They are equally important for the performance of the human immune system with the continuous recirculation of leukocytes from the tissues via lymphatics to the blood vessels and back into the tissue presenting the link between both systems. This study was undertaken to elucidate the differences in the gene expression between primary blood- and lymphatic endothelial cells as well as the two immortalized cell lines HMEC-1 (human microvascular endothelial cell line 1) and TIME (telomerase immortalized microvascular endothelial cell line). Furthermore, we wanted to investigate the mystery surrounding the identity of the antigen recognized by the prototype blood vascular marker PAL-E. In the last step we wanted to study whether the PAL-E antigen would be involved in the process of leukocyte migration from the bloodstream into the surrounding tissue. Our results clearly show that the gene expression in primary blood endothelial cells (BEC), lymphatic endothelial cells (LEC) and the cell lines HMEC-1 and TIME is plastic. Comparison of a large set of BEC- and LEC datasets allowed us to assemble a catalog of new, stable BEC- or LEC specific markers, which we verified in independent experiments. Additionally, several lines of evidence demonstrated that PAL-E recognizes plasmalemma vesicle associated protein 1 (PV-1), which can form complexes with vimentin and neuropilin-1. Finally, numerous in vitro and in vivo experiments identify the first function of the protein PV-1 during leukocyte trafficking, where it acts as regulatory molecule.

The effects of location, feedstock availability, and supply-chain logistics on the greenhouse gas emissions of forest-biomass energy utilization in Finland

Forest biomass represents a geographically distributed feedstock, and geographical location affects the greenhouse gas (GHG) performance of a given forest-bioenergy system in several ways. For example, biomass availability, forest operations, transportation possibilities and the distances involved, biomass end-use possibilities, fossil reference systems, and forest carbon balances all depend to some extent on location. The overall objective of this thesis was to assess the GHG emissions derived from supply and energy-utilization chains of forest biomass in Finland, with a specific focus on the effect of location in relation to forest biomass’s availability and the transportation possibilities. Biomass availability and transportation-network assessments were conducted through utilization of geographical information system methods, and the GHG emissions were assessed by means of lifecycle assessment. The thesis is based on four papers in which forest biomass supply on industrial scale was assessed. The feedstocks assessed in this thesis include harvesting residues, smalldiameter energy wood and stumps. The principal implication of the findings in this thesis is that in Finland, the location and availability of biomass in the proximity of a given energyutilization or energy-conversion plant is not a decisive factor in supply-chain GHG emissions or the possible GHG savings to be achieved with forest-biomass energy use. Therefore, for the greatest GHG reductions with limited forest-biomass resources, energy utilization of forest biomass in Finland should be directed to the locations where most GHG savings are achieved through replacement of fossil fuels. Furthermore, one should prioritize the types of forest biomass with the lowest direct supply-chain GHG emissions (e.g., from transport and comminution) and the lowest indirect ones (in particular, soil carbon-stock losses), regardless of location. In this respect, the best combination is to use harvesting residues in combined heat and power production, replacing peat or coal.

The role of potassium in the corrosion of superheater materials in boilers firing biomass

Inhibition of global warming has become one of the major goals for the coming decades. A key strategy is to replace fossil fuels with more sustainable fuels, which has generated growing interest in the use of waste-derived fuels and of biomass fuels. However, from the chemical point of view, biomass is an inhomogeneous fuel, usually with a high concentration of water and considerable amounts of potassium and chlorine, all of which are known to affect the durability of superheater tubes. To slow down or reduce corrosion, power plants using biomass as fuel have been forced to operate at lower steam temperatures as compared to fossil fuel power plants. This reduces power production efficiency: every 10°C rise in the steam temperature results in an approximate increase of 2% in power production efficiency. More efficient ways to prevent corrosion are needed so that power plants using biomass and waste-derived fuels can operate at higher steam temperatures. The aim of this work was to shed more light on the alkali-induced corrosion of superheater steels at elevated temperatures, focusing on potassium chloride, the alkali salt most frequently encountered in biomass combustion, and on potassium carbonate, another potassium salt occasionally found in fly ash. The mechanisms of the reactions between various corrosive compounds and steels were investigated. Based on the results, the potassium-induced accelerated oxidation of chromia protected steels appears to occur in two consecutive stages. In the first, the protective chromium oxide layer is destroyed through a reaction with potassium leading to the formation of intermediates such as potassium chromate (K2CrO4) and depleting the chromium in the protective oxide layer. As the chromium is depleted, chromium from the bulk steel diffuses into the oxide layer to replenish it. In this stage, the ability of the material to withstand corrosion depends on the chromium content (which affects how long it takes the chromium in the oxide layer to be depleted) and on external factors such as temperature (which affects how fast the chromium diffuses into the protective oxide from the bulk steel). For accelerated oxidation to continue, the presence of chloride appears to be essential.