Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH,) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH4 and CO2 of around 340degreesC for Nisyros and 470degreesC for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H2O-H-2-CO2-CO-CH4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH4, CO2 and H2O implying that carbon isotope partitioning between CO2 and CH, in both systems is controlled by aquifer temperature. N-2/(3) He and CH4/(3) He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH4 may have been primarily generated through the reduction of CO, by H, in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH4 and subsequent re-equilibration with co-existing CO2 cannot be ruled out entirely- CO2/He-3 ratios and delta(13)C(CO2) values imply that the evolved CO2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH4 during thermometamorphism. Copyright (C) 2004 Elsevier Ltd.

The Effect of Adding CO2 to Hypoxic Inspired Gas on Cerebral Blood Flow Velocity and Breathing during Incremental Exercise

Hypoxia increases the ventilatory response to exercise, which leads to hyperventilation-induced hypocapnia and subsequent reduction in cerebral blood flow (CBF). We studied the effects of adding CO2 to a hypoxic inspired gas on CBF during heavy exercise in an altitude naïve population. We hypothesized that augmented inspired CO2 and hypoxia would exert synergistic effects on increasing CBF during exercise, which would improve exercise capacity compared to hypocapnic hypoxia. We also examined the responsiveness of CO2 and O2 chemoreception on the regulation ventilation (E) during incremental exercise. We measured middle cerebral artery velocity (MCAv; index of CBF), E, end-tidal PCO2, respiratory compensation threshold (RC) and ventilatory response to exercise (E slope) in ten healthy men during incremental cycling to exhaustion in normoxia and hypoxia (FIO2 = 0.10) with and without augmenting the fraction of inspired CO2 (FICO2). During exercise in normoxia, augmenting FICO2 elevated MCAv throughout exercise and lowered both RC onset andE slope below RC (P<0.05). In hypoxia, MCAv and E slope below RC during exercise were elevated, while the onset of RC occurred at lower exercise intensity (P<0.05). Augmenting FICO2 in hypoxia increased E at RC (P<0.05) but no difference was observed in RC onset, MCAv, or E slope below RC (P>0.05). The E slope above RC was unchanged with either hypoxia or augmented FICO2 (P>0.05). We found augmenting FICO2 increased CBF during sub-maximal exercise in normoxia, but not in hypoxia, indicating that the 'normal' cerebrovascular response to hypercapnia is blunted during exercise in hypoxia, possibly due to an exhaustion of cerebral vasodilatory reserve. This finding may explain the lack of improvement of exercise capacity in hypoxia with augmented CO2. Our data further indicate that, during exercise below RC, chemoreception is responsive, while above RC the ventilatory response to CO2 is blunted.

Emission Trading and Tradable Green Certificates Impacts on the Business Activity of Vattenfall Oy

Ihmisen toiminnan vaikutus ilmakehään johtaa todennäköisesti ilmastonmuutoksiin. Eräs näistä muutoksista on maapallon keskilämpötilan nousu, joka aiheutuu kasvihuonekaasujen lisääntyneestä pitoisuudesta ilmakehässä. Vaikutusten vähentämiseksi on hiilidioksidipäästöjä vähennettävä. Kioton pöytäkirja asettaa allekirjoittaneille maille päästövelvoitteet. Euroopan unionin tulee vähentää kasvihuonekaasupäästöjään 8%:lla. Eräs vähennysmekanismeista on päästökauppa. Päästökauppa on sekä keino suojella ympäristöä että ympäristöpoliittinen instrumentti kasvihuonekaasupäästövähennysten kustannusten keventämiseksi. Päästökauppa ei suoranaisesti vähennä kasvihuonekaasupäästöjä, vaan tasaa niitä maiden ja laitosten välillä. Uusiutuvan energian käytön edistäminen sekä kansainvälisesti että kansallisesti johtaa suoriin kasvihuonekaasupäästöjen vähenemiseen. Euroopan unionin jäsenvaltiot ovat asettaneet kansalliset viitearvot uusituvan sähkön kulutukselle. Saavuttaakseen nämä viitearvot maiden tulee tukea uusiutuvia energialähteitä eri menetelmin kuten vihreillä sertifikaateilla. Päästökauppa ja kaupattavat vihreät sertifikaatit tulevat vaikuttamaan energiantuottajien liiketoimintaan. Työssä on tutkittu päästökaupan ja vihreiden sertifikaattien vaikutuksia Vattenfall Kaukolämpö Oy:n, Vattenfall Sähköntuotanto Oy:n ja Vamy Oy:n liiketoimintaan.

CO2-päästötaseenhallinta terästeollisuudessa

Tämän diplomityön tavoitteena oli kehittää hiilidioksiditaseen hallintamenetelmää Rautaruukin toiminnoille päästökaupan olosuhteissa. Taseenhallintamenetelmä sisältää päästöjen laskennan sekä päästöoikeuksien hallintaan liittyviä asioita. EU:n laajuisen päästökaupan reunaehdot määrittelee päästökauppadirektiivi ja sen antama päästöjen seurantaa ja raportointia koskeva monitorointiohje. Työssä on tarkasteltu hiilidioksidipäästöhistoriaa ja laskentamenetelmiä niiden Rautaruukin toimipaikkojen kohdalta, joiden oletetaan kuuluvan EU:n päästökaupan piiriin. Toimipaikoista on tarkasteltu erityisesti Raahen ja Koverharin terästehtaita, sillä ne muodostavat merkittävimmän osuuden konsernin Suomen toimipaikkojen hiilidioksidipäästöistä. Muita tarkasteltavia toimipaikkoja ovat Hämeenlinnan ja Dalsbrukin valssaamot Suomessa, Smedjebackenin terästehdas ja Boxholmin valssaamo Ruotsissa, Mo i Ranan terästehdas ja Profilerin valssaamo Norjassa sekä Nedstaalin valssaamo Hollannissa. Kustannustehokkaan ja hallitun päästökaupankäynnin perustaksi yritystasolla tarvitaan päästötaseenhallintamenetelmä, jonka avulla voidaan määrittää syntyneet päästöt komission monitorointiohjeen vaatimalla tavalla, arvioida tulevia päästömääriä sekä hallita päästökaupankäyntiä. Päästökaupanhallintaan sisältyviä asioita ovat saadut ilmaiset päästöoikeudet, ostettavien tai myytävien oikeuksien määrä, kaupankäynnin ajankohta, päästöoikeuksien erilaiset hankintamahdollisuudet, päästöoikeuksien hinnanmuodostus ja riskienhallinta.

Histologic evaluation of thermal damage produced on soft tissues by CO2, Er,Cr:YSGG and diode lasers

Objective: The aim of this in vitro experimental study was to perform histological evaluation of the thermal effect produced on soft tissue irradiated with CO2, Er,Cr:YSGG or diode lasers. Study design: Porcine oral mucosa samples were irradiated with Er,Cr:YSGG laser at 1 W with and without water / air spray, at 2 W with and without water / air spray, and at 4 W with water / air spray, with CO2 laser at 1 W, 2 W, 10 W, 20 W continuous mode and 20 W pulsed mode and diode laser at 2W, 5W, and 10W pulsed mode. The thermal effect was evaluated measuring the width of damaged tissue adjacent to the incision, stained positively for hyalinized tissue with Hematoxylin-Eosin and Masson Trichrome stains. Besides, histological changes in the irradiated tissue were described using subjective grading scales. Results: The evaluated lasers developed a wide range of thermal damage with significant differences between groups. The samples with lowest thermal effect were those irradiated with Er,Cr:YSGG laser using water / air spray, followed by CO2 and diode lasers. Conclusions: Emission parameters of each laser system may influence the thermal damage inflicted on the soft tissue, however, the wave length of each laser determines the absorption rate characteristics of every tissue and the thermal effect

Monte Carlo simulation of x-ray emission by kilovolt electron bombardment

A physical model for the simulation of x-ray emission spectra from samples irradiated with kilovolt electron beams is proposed. Inner shell ionization by electron impact is described by means of total cross sections evaluated from an optical-data model. A double differential cross section is proposed for bremsstrahlung emission, which reproduces the radiative stopping powers derived from the partial wave calculations of Kissel, Quarles and Pratt [At. Data Nucl. Data Tables 28, 381 (1983)]. These ionization and radiative cross sections have been introduced into a general-purpose Monte Carlo code, which performs simulation of coupled electron and photon transport for arbitrary materials. To improve the efficiency of the simulation, interaction forcing, a variance reduction technique, has been applied for both ionizing collisions and radiative events. The reliability of simulated x-ray spectra is analyzed by comparing simulation results with electron probe measurements.

Management of Nitrogen Oxides Reduction Project in a Cement Plant

The main aim of this study was to develop the project management framework model which would serve as the new model to follow for upcoming projects at the Lappeenranta cement plant. The other goal was to execute the SNCR (selective non catalytic reduction) project successfully so that the nitrogen oxides emissions are below the stated emission limit when the new emission limit comes into effect beginning in July, 2008. Nitrogen oxides, project management aspects, SNCR and the invested system are explained in the theory part. In the practical part of the study, the SNCR project in the Lappeenranta cement plant was executed and the findings were documented. In order to reach the aim of this study, a framework of project management was made. The framework is based on the executed SNCR project, previous projects in the cement plant and on the available literature relating to the subject matter. The developed project turned out to be successful.

Small scale energy production in Helsinki Metropolitan area in emission trading point of view

Emission trading with greenhouse gases and green certificates are part if the climate policy the main target of which is reduce greenhouse gas emissions. The carbon dioxide and fine particle emissions of energy production in Helsinki Metropolitan area are calculated in this study. The analysis is made mainly by district heating point of view and the changes of the district heating network are assessed. Carbon dioxide emissions would be a bit higher, if the district heating network is expanded, but then the fine particle emissions would be much lower. Carbon dioxide emissions are roughly 10 % higher, if the district heating network is expanded at same rate as it has in past five years in the year 2030. The expansion of district heating network would decrease the fine particle emissions about 40 %. The cost of the expansion is allocated to be reduction cost of the fine particle emissions, which is considerably higher than the traditional reduction methods costs. The possible new nuclear plant would reduce the emissions considerably and the costs of the nuclear plant would be relatively low comparing the other energy production methods.

Empirics of the international inequality in CO2 emissions intensity: explanatory factors according to complementary decomposition methodologies

This paper analyses the international inequalities in CO2 emissions intensity for the period 1971- 2009 and assesses explanatory factors. Multiplicative, group and additive methodologies of inequality decomposition are employed. The first allows us to clarify the separated role of the carbonisation index and the energy intensity in the pattern observed for inequalities in CO2 intensities; the second allows us to understand the role of regional groups; and the third allows us to investigate the role of different fossil energy sources (coal, oil and gas). The results show that, first, the reduction in global emissions intensity has coincided with a significant reduction in international inequality. Second, the bulk of this inequality and its reduction are attributed to differences between the groups of countries considered. Third, coal is the main energy source explaining these inequalities, although the growth in the relative contribution of gas is also remarkable. Fourth, the bulk of inequalities between countries and its decline are explained by differences in energy intensities, although there are significant differences in the patterns demonstrated by different groups of countries.

Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

Crop residues on short-term CO2 emissions in sugarcane production areas

The proper management of agricultural crop residues could produce benefits in a warmer, more drought-prone world. Field experiments were conducted in sugarcane production areas in the Southern Brazil to assess the influence of crop residues on the soil surface in short-term CO2 emissions. The study was carried out over a period of 50 days after establishing 6 plots with and without crop residues applied to the soil surface. The effects of sugarcane residues on CO2 emissions were immediate; the emissions from residue-covered plots with equivalent densities of 3 (D50) and 6 (D100) t ha-1 (dry mass) were less than those from non-covered plots (D0). Additionally, the covered fields had lower soil temperatures and higher soil moisture for most of the studied days, especially during the periods of drought. Total emissions were as high as 553.62 ± 47.20 g CO2 m-2, and as low as 384.69 ± 31.69 g CO2 m-2 in non-covered (D0) and covered plot with an equivalent density of 3 t ha-1 (D50), respectively. Our results indicate a significant reduction in CO2 emissions, indicating conservation of soil carbon over the short-term period following the application of sugarcane residues to the soil surface.

Influences of two CO2 concentrations and water availability on bean crop

This study was carried out to determine some physiological and phenological responses of the bean under high [CO2] and drought stress. The experiment was conducted from April to July 2009 in Viçosa, Brazil. The open-top chambers were used to enrich the air with CO2, whereas the drought stress was applied between the flowering and the ripening. The randomized block design was used, with four replicates in the subplots. The following plots were [CO2] at 700ppm (F1) and [CO2] environmental (F2) and the subplots were well watering (S1) and drought stress (S2). The results were subjected to Anova and the Tukey test (P < 0.05). For the treatments F1S1 and F1S2 the photosynthetic rate showed increments of 59% and the transpiration reduction of 12%. The yield, leaf temperature and stomatal conductance were not significant different to high [CO2], different from the dry matter, who showed increment of 20% (F1S1) and the water use efficiency who showed increase of 90% for high [CO2]. The osmotic potential was lower in plants under drought stress (F2S2 and F1S2), followed by plants under high [CO2] (F1S1). Despite the increment in photosynthesis, high [CO2] does not guarantee higher yield.

Fracture modes and acoustic emission characteristics of hydrogen-assisted cracking in high-strength low-alloy steel weldment

The aim of the present paper is to study the relationship between the fracture modes in hydrogen-assisted cracking (HAC) in microalloied steel and the emission of acoustic signals during the fracturing process. For this reason, a flux-cored arc weld (FCAW) was used in a high-strength low-alloy steel. The consumable used were the commercially available AWS E120T5-K4 and had a diameter of 1.6 mm. Two different shielding gases were used (CO2 and CO2+5% H2) to obtain complete phenomenon characterization. The implant test was applied with three levels of restriction stresses. An acoustic emission measurement system (AEMS) was coupled to the implant test apparatus. The output signal from the acoustic emission sensor was passed through an electronic amplifier and processed by a root mean square (RMS) voltage converter. Fracture surfaces were examined by scanning electron microscopy (SEM) and image analysis. Fracture modes were related with the intensity, the energy and the number of the peaks of the acoustic emission signal. The shielding gas CO2+5% H2 proved to be very useful in the experiments. Basically, three different fracture modes were identified in terms of fracture appearance: microvoid coalescence (MVC), intergranular (IG) and quasi-cleavage (QC). The results show that each mode of fracture presents a characteristic acoustic signal.

Towards sustainable Iron- and steelmaking with economic optimization

The iron and steelmaking industry is among the major contributors to the anthropogenic emissions of carbon dioxide in the world. The rising levels of CO2 in the atmosphere and the global concern about the greenhouse effect and climate change have brought about considerable investigations on how to reduce the energy intensity and CO2 emissions of this industrial sector. In this thesis the problem is tackled by mathematical modeling and optimization using three different approaches. The possibility to use biomass in the integrated steel plant, particularly as an auxiliary reductant in the blast furnace, is investigated. By pre-processing the biomass its heating value and carbon content can be increased at the same time as the oxygen content is decreased. As the compression strength of the preprocessed biomass is lower than that of coke, it is not suitable for replacing a major part of the coke in the blast furnace burden. Therefore the biomass is assumed to be injected at the tuyere level of the blast furnace. Carbon capture and storage is, nowadays, mostly associated with power plants but it can also be used to reduce the CO2 emissions of an integrated steel plant. In the case of a blast furnace, the effect of CCS can be further increased by recycling the carbon dioxide stripped top gas back into the process. However, this affects the economy of the integrated steel plant, as the amount of top gases available, e.g., for power and heat production is decreased. High quality raw materials are a prerequisite for smooth blast furnace operation. High quality coal is especially needed to produce coke with sufficient properties to ensure proper gas permeability and smooth burden descent. Lower quality coals as well as natural gas, which some countries have in great volumes, can be utilized with various direct and smelting reduction processes. The DRI produced with a direct reduction process can be utilized as a feed material for blast furnace, basic oxygen furnace or electric arc furnace. The liquid hot metal from a smelting reduction process can in turn be used in basic oxygen furnace or electric arc furnace. The unit sizes and investment costs of an alternative ironmaking process are also lower than those of a blast furnace. In this study, the economy of an integrated steel plant is investigated by simulation and optimization. The studied system consists of linearly described unit processes from coke plant to steel making units, with a more detailed thermodynamical model of the blast furnace. The results from the blast furnace operation with biomass injection revealed the importance of proper pre-processing of the raw biomass as the composition of the biomass as well as the heating value and the yield are all affected by the pyrolysis temperature. As for recycling of CO2 stripped blast furnace top gas, substantial reductions in the emission rates are achieved if the stripped CO2 can be stored. However, the optimal recycling degree together with other operation conditions is heavily dependent on the cost structure of CO2 emissions and stripping/storage. The economical feasibility related to the use of DRI in the blast furnace depends on the price ratio between the DRI pellets and the BF pellets. The high amount of energy needed in the rotary hearth furnace to reduce the iron ore leads to increased CO2 emissions.

Potential for Greenhouse Gas Emission Reductions by Using Biomethane as a Road Transportation Fuel

The aim of this thesis is to study whether the use of biomethane as a transportation fuel is reasonable from climate change perspective. In order to identify potentials and challenges for the reduction of greenhouse gas (GHG) emissions, this dissertation focuses on GHG emission comparisons, on feasibility studies and on the effects of various calculation methodologies. The GHG emissions calculations are carried out by using life cycle assessment (LCA) methodologies. The aim of these LCA studies is to figure out the key parameters affecting the GHG emission saving potential of biomethane production and use and to give recommendations related to methodological choices. The feasibility studies are also carried out from the life cycle perspective by dividing the biomethane production chain for various operators along the life cycle of biomethane in order to recognize economic bottlenecks. Biomethane use in the transportation sector leads to GHG emission reductions compared to fossil transportation fuels in most cases. In addition, electricity and heat production from landfill gas, biogas or biomethane leads to GHG reductions as well. Electricity production for electric vehicles is also a potential route to direct biogas or biomethane energy to transportation sector. However, various factors along the life cycle of biomethane affect the GHG reduction potentials. Furthermore, the methodological selections have significant effects on the results. From economic perspective, there are factors related to different operators along the life cycle of biomethane, which are not encouraging biomethane use in the transportation sector. To minimize the greenhouse gas emissions from the life cycle of biomethane, waste feedstock should be preferred. In addition, energy consumption, methane leakages, digestate utilization and the current use of feedstock or biogas are also key factors. To increase the use of biomethane in the transportation sector, political steering is needed to improve the feasibility for the operators. From methodological perspective, it is important to recognize the aim of the life cycle assessment study. The life cycle assessment studies can be divided into two categories: 1.) To produce average GHG information of biomethane to evaluate the acceptability of biomethane use compared to fossil transportation fuels. 2.) To produce GHG information of biomethane related to actual decision-making situations. This helps to figure out the actual GHG emission changes in cases when feedstock, biogas or biomethane are already in other use. For example directing biogas from electricity production to transportation use does not necessarily lead to additional GHG emission reductions. The use of biomethane seems to have a lot of potential for the reduction of greenhouse gas emissions as a transportation fuel. However, there are various aspects related to production processes, to the current use of feedstock or biogas and to the feasibility that have to be taken into account.