Metsäteollisuuden sivuainevirtojen käsittely- ja hyödyntämisvaihtoehtojen vaikutus hiilidioksidipäästöihin

Tämä tutkimus kuuluu ympäristöklusterin tutkimusprojektiin "Materiaalivirrat ja energiankäyttö metsäteollisuusintegraateissa ja niihin liittyvät toimintastrategiat ympäristövaikutuslähtöisesti". Työn päätavoitteena oli kehittää laskentapohja, jossa alkuarvoja muuttamalla voidaan helposti määritellä metsäteollisuuden jäte- eli sivuainevirtojen käsittelystä ja hyötykäytöstä aiheutuvia hiilidioksidivaikutuksia. Tutkimuksen sisältö pohjautuu pääosin projektin muihin tutkimuksiin, joissa on tarkasteltu sivuainevirtojen hyötykäytön teknisiä ja taloudellisia reunaehtoja. Metsäteollisuuden tärkeimmiksi sivuainevirroiksi voidaan määritellä tuhka, soodasakka, jätevedenkäsittelyn liete sekä pastaliete. Tässä tutkimuksessa on laskettu näiden sivuainevirtojen nykyisten käsittelymenetelmien hiilidioksidivaikutukset projektissa mukana olevilla tehtailla ja vertailtu niitä potentiaalisempien uusien käsittely- ja hyötykäyttömenetelmien vaikutuksiin. Työstä saatujen tulosten perusteella voidaan arvioida, että tuhkan osalta hiilidioksidivaikutukset ovat suhteellisen merkityksettömiä. Pastalietteen osalta prosessiin palautus vaikuttaisi parhaalta menetelmältä, koska tuorepastan tuotannosta aiheutuu varsin runsaasti hiilidioksidipäästöjä. Suurin merkitys kokonaispäästöjen kannalta näyttäisi kuitenkin olevan jätevedenkäsittelyn lietteen ja soodasakan käsittelymenetelmillä. Soodasakan orgaaninen aines aiheuttaa kaatopaikoilla suurehkot metaanipäästöt, joita hyötykäytöllä voitaisiin vähentää merkittävästi. Jätevedenkäsittelyn lietteen osalta uudet kuivauksen tehostamismenetelmät parantavat lietteen poltettavuutta, jolloin myös hiilidioksidipäästöt pienenevät. Toisaalta suuremman kuiva-ainepitoisuuden vuoksi myös varastointi voisi olla mahdollista, jolloin lietettä ei tarvitsisi läjittää enää kaatopaikoille, ja myös kaatopaikkapäästöiltä vältyttäisiin.

Unconventional Determinants of Greenhouse Gas Emissions: The Role of Trust

[cat] Les normes socials han estat incloses en la teoria de l’acció col.lectiva per a superar les dificultats per explicar perquè la gestió del béns comuns podria ser més efectiva quan s’autoregula per les mateixes comunitats. El paper rellevant de la confiança en els altres s’ha identificat en diversos contextos d’acció social a nivell local, però només recentment s’ha considerat la idea que també podria ser rellevant en el cas de béns comuns de caire global, seguint l’evidència bàsicament descriptiva recollida per Elinor Ostrom. Però fins ara no hi havia proves quantitatives disponibles d’aquesta idea. Utilitzant un conjunt de dades de 29 països europeus durant el període 1990-2007, donem evidència empírica a favor del paper del nivell de confiança en els altres en el context dels béns públics globals. Concloem que el nivell de confiança en els altres té un impacte reductor de les emissions de gasos d’efecte hivernacle; per exemple, l’extrapolació dels resultats implicaria una reducció d’emissions d’Espanya del 12,5% si el nivell mitjà de confiança en els altres dels espanyols fos tan elevat com els dels suecs.

Rinnakkaispolttolaitoksen ympäristöntarkkailusuunnitelma

Diplomityössä päivitetään voimalaitoksen ympäristöntarkkailusuunnitelma vastaamaan uudistuneen ympäristöluvan ja lainsäädännön edellytyksiä. Työssä tutkitaan leijupetikatti-loiden tulipesän lämpötiloja, savukaasun viipymäaikoja tulipesässä, leijukerroskattiloiden päästöjä, päästöjen jatkuvatoimista mittaamista sekä päästöjen seurantaa ja raportointia. Tulipesän lämpötiloja mitattiin kupla- ja kiertoleijukattiloilla. Tuloksien perusteella havait-tiin kiertoleijukattilan tulipesän alaosan lämpötilojen olevan lähes riippumaton pedin lämpötilasta ja höyrykuormasta. Tulipesän yläosassa lämpötilat nousevat höyrykuorman kasvaessa, mutta pedin lämpötilalla ei havaittu vaikutusta tulipesän yläosassakaan. Molemmilla kattiloilla havaittiin voimakas vaakatasoinen lämpötilaprofiili. Kuplaleijukattilalla sekä höyrykuorma että pedin lämpötila vaikuttivat tulipesän lämpötilaan. Savukaasun teoreettiset viipymäajat laskettiin kiertoleijukattilalle. Laskelmien ja mittauksien perusteella havaittiin kattilalla mahdollisuus saavuttaa savukaasun kahden sekunnin viipymäaika 850 ºC lämpötilassa. Kattilan käyttäytymisen aukottomaksi selvittämiseksi kaikilla polttoaineseoksilla ja höyrykuormilla tarvitaan lisää toimenpiteitä kattilalla ja lisää tulipesän lämpötilamittauksia. Leijukerroskattiloiden päästöjen syntymistä ja hallintaa tutkittiin teoreettisesti kirjallisuustutkimuksena. Tutkittuihin päästöihin kuuluivat typen oksidit, rikkidioksidi, hiukkaset, hiilimonoksidi, orgaaninen kokonaishiili, suolahappo, fluorivety, raskasmetallit sekä dioksiinit ja furaanit. Jatkuvatoimisten päästömittausmittauslaitteiden toimintaperiaatteita selvitettiin kirjalli-suustutkimuksena. Samoin selvitettiin jatkuvatoimisten päästömittauslaitteiden virhelähtei-tä. Päästömittauslaitteille laadittiin pitkän ja lyhyen ajan laadunvarmistussuunnitelma. Ha-vaittiin, että nykyiset jatkuvatoimiset päästömittauslaitteet eivät täytä kaikkia uusia laatu-kriteereitä. Päästöjen jatkuvatoimiseen seuraamiseen työssä suunniteltiin uusi valvomonäyttö. Uuden näytön avulla tehostetaan päästöjen valvontaa. Päästöjen raportointiin työssä suunniteltiin vuorokausiraportti. Raporttiin kerätään jatkuva-toimisten päästömittauslaitteiden puolen tunnin keskiarvot. Raportin tarkastaa, allekirjoittaa ja arkistoi vuorossa oleva operaattori.

Environmental Structural Decomposition Analysis of Italian Emissions, 1995-2005

[spa] El estudio analiza la evolución de los gases de efecto invernadero (GEI) y las emisiones de acidificación para Italia durante el periodo 1995-2005. Los datos muestran que mientras las emisiones que contribuyen a la acidificación han disminuido constantemente, las emisiones de GEI han aumentado debido al aumento de dióxido de carbono. El objetivo de este estudio es poner de relieve cómo diferentes factores económicos, en particular el crecimiento económico, el desarrollo de una tecnología menos contaminante y la estructura del consumo, han impulsado la evolución de las emisiones. La metodología propuesta es un análisis de descomposición estructural (ADE), método que permite descomponer los cambios de la variable de interés entre las diferentes fuerzas y revelar la importancia de cada factor. Por otra parte, este estudio considera la importancia del comercio internacional e intenta incluir el “problema de la responsabilidad”. Es decir, a través de las relaciones comerciales internacionales, un país podría estar exportando procesos de producción contaminantes sin una reducción real de la contaminación implícita en su patrón de consumo. Con este fin, siguiendo primero un enfoque basado en la “responsabilidad del productor”, el ADE se aplica a las emisiones causadas por la producción nacional. Sucesivamente, el análisis se mueve hacia un enfoque basado en la “responsabilidad del consumidor" y la descomposición se aplica a las emisiones relacionadas con la producción nacional o la producción extranjera que satisface la demanda interna. De esta manera, el ejercicio permite una primera comprobación de la importancia del comercio internacional y pone de relieve algunos resultados a nivel global y a nivel sectorial.

Environmental Structural Decomposition Analysis of Italian Emissions, 1995-2005

[spa] El estudio analiza la evolución de los gases de efecto invernadero (GEI) y las emisiones de acidificación para Italia durante el periodo 1995-2005. Los datos muestran que mientras las emisiones que contribuyen a la acidificación han disminuido constantemente, las emisiones de GEI han aumentado debido al aumento de dióxido de carbono. El objetivo de este estudio es poner de relieve cómo diferentes factores económicos, en particular el crecimiento económico, el desarrollo de una tecnología menos contaminante y la estructura del consumo, han impulsado la evolución de las emisiones. La metodología propuesta es un análisis de descomposición estructural (ADE), método que permite descomponer los cambios de la variable de interés entre las diferentes fuerzas y revelar la importancia de cada factor. Por otra parte, este estudio considera la importancia del comercio internacional e intenta incluir el “problema de la responsabilidad”. Es decir, a través de las relaciones comerciales internacionales, un país podría estar exportando procesos de producción contaminantes sin una reducción real de la contaminación implícita en su patrón de consumo. Con este fin, siguiendo primero un enfoque basado en la “responsabilidad del productor”, el ADE se aplica a las emisiones causadas por la producción nacional. Sucesivamente, el análisis se mueve hacia un enfoque basado en la “responsabilidad del consumidor" y la descomposición se aplica a las emisiones relacionadas con la producción nacional o la producción extranjera que satisface la demanda interna. De esta manera, el ejercicio permite una primera comprobación de la importancia del comercio internacional y pone de relieve algunos resultados a nivel global y a nivel sectorial.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

Characterization of volatile organic gunshot residues in fired handgun cartridges by headspace sorptive extraction

In forensic investigation of firearm-related cases, determination of the residual amount of volatile compounds remaining inside a cartridge could be useful in estimating the time since its discharge. Published approaches are based on following the decrease of selected target compounds as a function of time by using solid phase micro-extraction (SPME). Naphthalene, as well as an unidentified decomposition product of nitrocellulose (referred to as "TEA2"), are usually employed for this purpose. However, reliability can be brought into question given their high volatility and the low reproducibility of their extracted quantities. In order to identify alternatives and therefore develop improved dating methods, an extensive study on the composition and variability of volatile residues in nine different types of cartridges was carried out. Analysis was performed using headspace sorptive extraction (HSSE), which is a more exhaustive technique compared to SPME. 166 compounds were identified (several of which for the first time), and it was observed that the final compositional characteristics of each residue were strongly dependent on its source. Variability of single identified compounds within and between different types of cartridge, as well as their evolution over time, was also studied. Many explosion products containing up to 4 aromatic rings were found to be globally present in high proportions amongst residues. 27 of them (excluding naphthalene) also presented detectable decreases during the first 24 h. Therefore, they could be used as complementary target analytes in future dating methods.

Odor emission control and reduce in betaine manufacture

This thesis was made in Naantali plant of Finnfeeds Finland Oy. In this thesis the main study was in reducing, controlling, measuring and processing odour effluents in various methods. Also are considered legislation, marketing issues and environmental requirements of reducing of odour effluents. The literature review introduces odours complications, legislations and various methods of odour removal. There is also a review of volatile organic compounds detection and measuring methods. The experimental section consists TD-GC-MS-measurements and expansive measurements with electronic nose. Electronic nose is a new solution for recognition and measuring industrial odours. In this thesis the electronic nose was adapted into reliable recognition and measuring method. Measurements with electronic nose was made in betaine factory and main targets were odour removal process and other odours from factory. As a result of experimental work with TD-GC-MS-measurements becomes odour compound of 2-and 3- methylbutanal and dimethyldisulfide, which odour is sweet and fug. Extensive study with electronic nose found many developmental subjects. Odour balance measurements of factory and after calculation made adjustment of odour removal process, over all odour effluent to environment will reduce 25 %.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Transition mutation in codon 248 of the p53 tumor suppressor gene induced by reactive oxygen species and a nitric oxide-releasing compound.

Exposing the human bronchial epithelial cell line BEAS-2B to the nitric oxide (NO) donor sodium 1-(N,N-diethylamino)diazen-1-ium-1, 2-diolate (DEA/NO) at an initial concentration of 0.6 mM while generating superoxide ion at the rate of 1 microM/min with the hypoxanthine/xanthine oxidase (HX/XO) system induced C:G-->T:A transition mutations in codon 248 of the p53 gene. This pattern of mutagenicity was not seen by 'fish-restriction fragment length polymorphism/polymerase chain reaction' (fish-RFLP/PCR) on exposure to DEA/NO alone, however, exposure to HX/XO led to various mutations, suggesting that co-generation of NO and superoxide was responsible for inducing the observed point mutation. DEA/NO potentiated the ability of HX/XO to induce lipid peroxidation as well as DNA single- and double-strand breaks under these conditions, while 0.6 mM DEA/NO in the absence of HX/XO had no significant effect on these parameters. The results show that a point mutation seen at high frequency in certain common human tumors can be induced by simultaneous exposure to reactive oxygen species and a NO source.

Industrial emissions abatement: Untangling the impact of the EU ETS and the economic crisis

In this study we use historical emission data from installations under the European Union Emissions Trading System, -EU ETS- to evaluate the impact of this policy on industrial greenhouse gas emissions during the first two trading phases, 2005-2012. As such the analysis seeks to disentangle two causes of emission abatement: that attributable to the EU ETS and that attributable to the economic crisis that hit the EU in 2008/09. Using a panel data approach the estimated emissions reduction attributable to the EU ETS is about 21 per cent of the total emission abatement during the observation period. These results suggest therefore that the lion’s share of abatement was attributable to the effects of the economic crisis, a finding that has serious implications for future policy adjustments affecting core elements of the EU ETS, including the distribution of EU emission allowances.

L'oxalate: un déchet organique peu soluble, avec conséquences [Oxalate: a poorly soluble organic waste with consequences].

Oxalate is a highly insoluble metabolic waste excreted by the kidneys. Disturbances of oxalate metabolism are encountered in enteric hyperoxaluria (secondary to malabsorption, gastric bypass or in case of insufficient Oxalobacter colonization), in hereditary hyperoxaluria and in intoxication (ethylene glycol, vitamin C). Hyperoxaluria causes a large spectrum of diseases, from isolated hyperoxaluria to kidney stones and nephrocalcinosis formation, eventually leading to kidney failure and systemic oxalosis with life-threatening deposits in vital organs. New causes of hyperoxaluria are arising recently, in particular after gastric bypass surgery, which requires regular and preemptive monitoring. The treatment of hyperoxaluria involves reduction in oxalate intake and increase in calcium intake. Optimal urine dilution and supplementation with inhibitors of kidney stone formation (citrate) are required. Some conditions may need vitamin B6 supplementation, and the addition of probiotics might be useful in the future. Primary care physicians should identify cases of recurrent calcium oxalate stones and severe hyperoxaluria. Further management of hyperoxaluria requires specialized care.

Compound Heterozygous VSX2 Mutation Causing Bilateral Anophthalmia in a Consanguineous Egyptian Family

Purpose: To report the clinical and genetic study of a child with bilateral anophthalmia. Methods: A 14-year-old Egyptian boy, born from consanguineous parents, underwent a general and a full ophthalmological examination. Mutation screen of the A/M genes with recessive inheritance was done stepwise and DNA was analyzed by Sanger sequencing. Results: Bilateral anophthalmia, arachnodactyly of the feet and high arched palate were observed on general examination. The parents were first cousins and healthy. Sequencing analysis revealed a novel compound heterozygous mutation in one of the copy of exon 2 of VSX2 and a possible deletion of at least exon 2 on the other allele. Conclusions: A compound heterozygous VSX2 mutation associated with anophthalmia was identified in a patient from an Egyptian consanguineous family. This report brings the number of VSX2 mutation in anophthalmia/microphthalmia (A/M) to 13. Functional consequences of the reported changes still need to be characterized, as well as the percentage of A/M caused by mutations in the VSX2 gene. This family also shows that despite consanguinity, heterozygous mutations can also happen and one should not restrict the molecular analysis to homozygous mutations.