Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 silica in the determination of copper

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol for determination of Cu(II) ions in sugar cane spirit (cachaça) is described, based on differential pulse anodic stripping voltammetry (DPASV) procedure. The Cu(II) oxidation peak was observed at 0.03 V (vs. SCE) in phosphate solution (pH 3.0). The results were obtained using optimised conditions such as 100 mV pulse amplitude, 3 min accumulation time, 25 mV s-1 scan rate in phosphate solution pH 3.0, resulting in a linear dynamic range from 8.0 x 10-7 to 1.0 x 10-5 mol L-1 Cu(II) and a limit of detection 2.0 x10-7 mol L-1. Cu(II) spiked in a cachaça sample was determined with 102.5 % mean recovery at mmol L-1 level. Interference from other metallic cations present in the sample was avoided by the standard addition procedure.

Natural and synthetic fibres improving tensile strength and elongation of paper products

The theory part of the Master’s thesis introduces fibres with high tensile strength and elongation used in the production of paper or board. Strong speciality papers are made of bleached softwood long fibre pulp. The aim of the thesis is to find new fibres suitable for paper making to increase either tensile strength, elongation or both properties. The study introduces how fibres bond and what kind of fibres give the strongest bonds into fibre matrix. The fibres that are used the in manufacturing of non-wovens are long and elastic. They are longer than softwood cellulose fibres. The end applications of non-wovens and speciality papers are often the same, for instance, wet napkins or filter media. The study finds out which fibres are used in non-wovens and whether the same fibres could be added to cellulose pulp as armature fibres, what it would require for these fibres to be blended in cellulose, how they would bind with cellulose and whether some binding agents or thermal bonding, such as hot calendaring would be necessary. The following fibres are presented: viscose, polyester, nylon, polyethylene, polypropylene and bicomponent fibres. In the empiric part of the study the most suitable new fibres are selected for making hand sheets in laboratory. Test fibres are blended with long fibre cellulose. The test fibres are viscose (Tencel), polypropylene and polyethylene. Based on the technical values measured in the sheets, the study proposes how to continue trials on paper machine with viscose, polyester, bicomponent and polypropylene fibres.

Design of an adsorbent employing activated carbon fiber to remove lead

Zorflex® activated carbon fibers (ACF), reference FM100 198B, are used before and after an oxidizing procedure with H3PO4 to study the adsorption of Pb2+. The point of zero charge was determined for the modified and unmodified fiber giving values of 2.3 and 4.3, respectively. After oxidizing the ACF, the fiber showed to have a greater Pb2+ adsorption capacity in comparison with the unmodified fiber, which is related with the acid sites increase, where lead was mainly adsorbed. Determination of the BET area was carried out by nitrogen physisorption at 77K. ACFs presented superficial areas between 1000 and 1500 m²/g showing mostly, a microporous structure. The preliminary design of an adsorbent using the modified fiber is presented where the fiber superior physicochemical properties over the unmodified one are observed.

Synthesis and characterization of activated carbon fibers from Kevlar

Kevlar [poly (p-phenilylene terephtalamide)], was used as a precursor in the preparation of activated carbon fibers. For this intention, physical and chemical activations were carried out. Activated fibers were physically prepared from the carbonization of the Kevlar and its later activation with CO2 and steam of water, by the other hand; the chemically activated fibers were obtained by means of the impregnation of the material with phosphoric acid and their later carbonization. Different conditions were used and preliminary analyses of the precursor were taken into account (TGA-DTA / IR). The resulting fibers were characterized by N2 (77K) adsorption, infrared spectroscopy, SEM, and immersion calorimetry. Yields and Burn off were also evaluated. The results shows that if you want to synthesize activated carbon fibers from Kevlar strong conditions respect to the commonly used such as water steam, high phosphoric acid concentrations and methods of impregnation are the ones who allows the development of optimal surface areas and pore volumes.

Model based study of a calcium oxide looping process for post-combustion carbon dioxide capture

Calcium oxide looping is a carbon dioxide sequestration technique that utilizes the partially reversible reaction between limestone and carbon dioxide in two interconnected fluidised beds, carbonator and calciner. Flue gases from a combustor are fed into the carbonator where calcium oxide reacts with carbon dioxide within the gases at a temperature of 650 ºC. Calcium oxide is transformed into calcium carbonate which is circulated into the regenerative calciner, where calcium carbonate is returned into calcium oxide and a stream of pure carbon dioxide at a higher temperature of 950 ºC. Calcium oxide looping has proved to have a low impact on the overall process efficiency and would be easily retrofitted into existing power plants. This master’s thesis is done in participation to an EU funded project CaOling as a part of the Lappeenranta University of Technology deliverable, reactor modelling and scale-up tools. Thesis concentrates in creating the first model frame and finding the physically relevant phenomena governing the process.

Carbon footprint as part of a company’s external environmental communication

The aim of this thesis was to find out how the carbon footprint calculations can be utilized in the company’s external environmental communication, what is the demand for carbon footprint from the market, and how the other actors in the forest industry have approached the issue. The aim was to recognize the best practises to communicate carbon footprints and to find possibilities to extend the UPM-Kymmene Wood Oy’s mill specific carbon footprints. This research included a literature review, an inquiry to the UPM-Kymmene Wood Oy’s sales offices, and Internet survey concerning the external environmental communication in the forest industry and three small case studies based on mill specific parameters. The inquiry to the sales offices showed that the carbon footprint is not yet a common demand from the customers in the wood product sector. In addition, the Internet survey showed that generally in the forest industry, not much has been done concerning carbon footprint communication so far. The biggest challenge in carbon footprint communication is the variation in the knowledge level of the receivers. In addition btob and btoc communication situations demand a different approach to the issue. Carbon profile brochures developed in the company can be seen as suitable for btob communication situations. Case studies have shown that the contribution of final product transport to the overall carbon footprint was significant. It was recommended to include post mill transport in the carbon footprint information supplied to the btob customers. When discussing environmental communication on a general level it can be stated that a good external environmental communication is based on facts, is open and proactive and takes into account the needs of the receiver. However, the openness and the quality of external environmental communication are essentially strategic decisions. The significance of internal communication as well as the knowhow in the communication and marketing networks play a major role in achieving success in external environmental communication. Carbon footprints are only one part of good balanced external environmental communication. One specific environmental feature like carbon footprint should not be over emphasized to the detriment of other important environmental aspects.

Catalytic transformations of fatty acid derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

Växtoljor som utgör en förnybar naturresurs används som sådana eller i modifierade former i många industriella processer, som är av stor betydelse för vårt vardagliga liv. Växtoljor används i livsmedel, i kemiska och farmaceutiska produkter, i textilindustrin, för framställning av färgämnen och beläggningsmaterial samt som miljövänliga bränslekomponenter. Fetter och oljor hör till de äldsta kemiska komponenterna som utnyttjas av människan. De består huvudsakligen av glycerolestrar och fettsyror. Fetter och oljor har typiskt en kolkedja med kol-koldubbelbindningar samt karboxyl- och estergrupper, som kan genom hydrering eller dekarboxylering konverteras till nyttiga och miljövänliga produkter med hjälp av ädelmetallkatalysatorer. Aktivt kol (C) används som bärare på katalysatorerna. Väteaddition, d.v.s. hydrering av växtoljor har varit föremål för omfattande forskning i över hundra års tid. Hydreringen är en viktig process, för den tillämpas på produktion av fetter och margarin. Omättade fettsyror hydreras traditionellt på nickelbaserade heterogena katalysatorer. Samtidigt med en partiell hydrering av fettsyrorna och fettsyraestrarna som har två dubbelbindningar pågår också isomeringsreaktioner, vilka ger cis- och transisomerer av reaktantmolekylerna. Den största nackdelen med nickelkatalysatorerna är deras giftighet samt bildning av ohälsosamma transisomerer i reaktionsprodukterna. Dessutom deaktiveras nickelkatalysatorn snabbt p.g.a. att nickeltvålar bildas i reaktionsblandningen. Platinabaserade katalysatorer lider däremot inte av dessa begränsningar. Metaller i platinagruppen i det periodiska systemet studerades i detalj för att avslöja kinetiska effekter i hydreringen av cis-metyloleat. Palladium, rutenium, rhodium, platina och iridium användes som katalytiska metaller. Metallhalten på aktivkolbärare var 1 vikt-%. De olika platinametallerna undersöktes för att kartlägga konkurrerande hydrerings- och isomeringsrutter på metallerna. Det visade sig att metallerna i andra raden av det periodiska systemet (Ru, Rh, Pd) är aktivare i isomeringsprocesserna, medan metallerna i tredje raden (Ir, Pt) har en lägre aktivitet. Pd/C valdes bland platinametallerna, för att den är attraktiv ur ekonomisk synvinkel och den är mycket aktiv och selektiv, speciellt jämfört med nickel. Tyngdpunkten i arbetet var utvecklingen av en alternativ, palladiumbaserad hydreringsteknologi som skulle ersätta den traditionella teknologin som är baserad på användningen av nickelkatalysatorer. Palladiumbaserade katalysatorer kan återcirkuleras, de är aktivare och mera resistenta mot syror och de bildar mindre mängder av skadliga transisomerer. För att denna teknologi skall bli ekonomiskt hållbar och konkurrenskraftig, måste den basera sig på de bästa möjliga katalysatorerna, vilket innebär att en optimal kombination av hög aktivitet och selektivitet samt en lång livstid för katalysatorn krävs. Därför inkluderades teknologiska aspekter kraftigt i forskningen. Mycket arbete satsades på design av palladium på en mesoporös kolbärare och undersökning av korrelationerna mellan katalysatorns egenskaper och dess aktivitet i isomeriseringsreaktionerna och i hydreringen av kol-koldubbelbindningarna i reaktantmolekylen. Katalysatorerna karakteriserades med många fysikaliska och kemiska metoder (transmissionselektronmikroskopi (TEM), röntgendiffraktion (XRD), röntgenfotoelektronspektroskopi (XPS), temperaturprogrammerad reduktion (TPR), temperaturprogrammerad desorption (TPD) av kolmonoxid, kemisorption av kolmonoxid, fysisorption av kväve). Temperaturens, vätetryckets och katalysatorkoncentrationens inverkan på fettsyra- och isomersammansättningen hos de hydrerade oljorna bestämdes under kinetiska betingelser, i frånvaro av massöverföringseffekter. Syreavspjälkning genom fullständig dekarboxylering av karboxylgruppen i fettsyramolekylen är det hittills bästa sättet att framställa miljövänlig dieselolja, eftersom linjära paraffiner fås som reaktionsprodukter och en tillsats av dyr vätgas undviks. Deoxygeneringen undersöktes systematiskt på en Pd/C-katalysator (Sibunit) genom att använda mättade fettsyror C16-C20 och C22 som råvara. Produktmolekylen blev en dieselliknande kolvätemolekyl, med en kolatom färre än i utgångsmolekylen. Lika stora dekarboxyleringshastigheter observerades för rena, mättade fettsyror. En jämförelse av deoxygenereringshastigheterna för stearin-, olein- och linolsyra som råvara vid 300oC i närvaro av 1-volymprocent väte på mesoporös Pd/C (Sibunit) avslöjade att katalysatorns aktivitet och selektivitet ökade med en ökande mättningsgrad av reaktantmolekylen. Då stearinsyra användes som utgångsmolekyl, bestod huvudprodukterna av önskade C17-kolväten, medan mängden av aromatiska C17-komponenter ökade, då olein- och linolsyra användes som utgångsmolekyler. Katalysatordeaktiveringen var relativt påfallande vid deoxygeneringen av linolsyra så att endast 3% av fettsyrorna omsattes till produkter i 330 min. Deaktiveringen orsakades av aromatiska C17-komponenter samt av fettsyradimerer, som bildades via en Diels-Alderreaktion. Hydreringen av omättade fettsyror kan därför rekommenderas som ett primärt kemiskt steg i framställningen av miljövänliga dieselprodukter. Målet var också att öka förståelsen av palladiummetallernas roll i nanoskala, speciellt effekten av metallpartiklarna i katalytisk hydrering och deoxygenering. Pd/C-katalysatorer med lika stora halter av Pd syntetiserades och metallens dispersion på bärarmaterialet varierades systematiskt genom en kontrollerad uppväxt av palladiumnanopartiklar på aktiv kolbärare. Metalldispersionens effekt på hydrerings-hastigheten och cis-transförhållandet undersöktes i detalj. En optimal metalldispersion som gav den högsta dekarboxyleringshastigheten hittades. Massöverföringens inverkan på reaktionens hastighet studerades experimentellt och temperaturprogrammerad desorption av kolmonoxid från katalysatorytan undersöktes ingående. Hydrering av växtoljor genomfördes under satsvisa och kontinuerliga betingelser. Både finfördelat Pd/C och katalysatorgranulat användes i experimenten. Ett av målen med arbetet var uppskalningen av hydreringsprocesserna. Med tanke på stora produktionsvolymer var det logiskt att undersöka kontinuerliga hydrerings- och dekarboxyleringsteknologier. En kontinuerlig packad bäddreaktor studerades i laboratorieskala, vilket gav viktig information om katalysatorns långtidsstabilitet och deaktivering. Effekten av rena fettsyror och triglycerider som råvara samt metallpartikelstorleken och palladiumhalten studerades med hjälp av den kontinuerliga reaktorn. Produktionskapaciteten som erhölls med satsvis och kontinuerlig drift jämfördes. Dekarboxyleringen av stearinsyra undersöktes också i en kontinuerlig packad bädd. Omsättningsgraden blev 15% för en stabil katalysator.

Carbon sequestration and nutrient reserves under differen t land use systems

This study evaluated the contribution of agroforestry (AFS) and traditional systems to carbon sequestration and nutrient reserves in plants, litter and soil. The study was carried out in the semiarid region of Brazil in a long-term experiment on an experimental farm of the goat and sheep section of the Brazilian Agricultural Research Corporation (Embrapa). Two agroforestry systems were investigated: agrosilvopastoral (ASP) and forest-pasture areas (SP) as well as traditional agriculture management (TM), two areas left fallow after TM (six fallow years - F6 and nine fallow years - F9) and one area of preserved Caatinga vegetation (CAT). Soil, litter and plants were sampled from all areas and the contents of C, N, P, K, Ca and Mg per compartment determined. The AFS (ASP and SP) had higher nutrient stocks than the traditional and intermediate stocks compared to the preserved Caatinga. In the ASP, a relevant part of the nutrients extracted by crops is returned to the system by constant inputs of litter, weeding of herbaceous vegetation and cutting of the legume crops. After fallow periods of six and nine years, carbon and nutrient stocks in the compartments soil, litter and herbaceous plants were similar to those of the preserved Caatinga (CAT), but still lower than under natural conditions in the woody vegetation.

ABOVEGROUND AND BELOWGROUND BIOMASS AND CARBON ESTIMATES FOR CLONAL EUCALYPTUS TREES IN SOUTHEAST BRAZIL

Eucalyptus plantations represent a short term and cost efficient alternative for sequestrating carbon dioxide from the atmosphere. Despite the known potential of forest plantations of fast growing species to store carbon in the biomass, there are relatively few studies including precise estimates of the amount of carbon in these plantations. In this study it was determined the carbon content in the stems, branches, leaves and roots of a clonal Eucalyptus grandis plantation in the Southeast of Brazil. We developed allometric equations to estimate the total amount of carbon and total biomass, and produced an estimate of the carbon stock in the stand level. Altogether, 23 sample trees were selected for aboveground biomass assessment. The roots of 9 of the 23 sampled trees were partially excavated to assess the belowground biomass at a singletree level. Two models with DBH, H and DBH2H were tested. The average relative share of carbon content in the stem, branch, leaf and root compartments was 44.6%, 43.0%, 46.1% and 37.8%, respectively, which is smaller than the generic value commonly used (50%). The best-fit allometric equations to estimate the total amount of carbon and total biomass had DBH2H as independent variable. The root-to-shoot ratio was relatively stable (C.V. = 27.5%) probably because the sub-sample was composed of clones. Total stand carbon stock in the Eucalyptus plantation was estimated to be 73.38 MgC ha-1, which is within the carbon stock range for Eucalyptus plantations.

SOIL ORGANIC CARBON, CARBON STOCK AND THEIR RELATIONSHIPS TO PHYSICAL ATTRIBUTES UNDER FOREST SOILS IN CENTRAL AMAZONIA

ABSTRACT The soil carbon under Amazonian forests has an important roles in global changing, making information on the soil content and depths of these stocks are considerable interest in efforts to quantify soil carbon emissions to the atmosphere.This study quantified the content and soil organic carbon stock under primary forest up to 2 m depth, at different topographic positions, at Cuieiras Biological Reserve, Manaus/ ZF2, km 34, in the Central Amazon, evaluating the soil attributes that may influence the permanence of soil carbon. Soil samples were collected along a transect of 850 m on topographic gradient Oxisol (plateau), Ultisol (slope) and Spodosol (valley). The stocks of soil carbon were obtained by multiplying the carbon content, soil bulk density and trickiness of soil layers. The watershed was delimited by using STRM and IKONOS images and the carbon contend obtained in the transects was extrapolated as a way to evaluate the potential for carbon stocks in an area of 2678.68 ha. The total SOC was greater in Oxisol followed by Spodosol and Ultisol. It was found direct correlations between the SOC and soil physical attributes. Among the clay soils (Oxisol and Ultisol), the largest stocks of carbon were observed in Oxisol at both the transect (90 to 175.5 Mg C ha-1) as the level of watershed (100.2 to 195.2 Mg C ha-1). The carbon stocks under sandy soil (Spodosol) was greater to clay soils along the transect (160-241 Mg C ha-1) and near them in the Watershed (96.90 to 146.01 Mg C ha-1).

Surface chemistry of fibres and vessel elements in chemical and recycled pulps

Den viktigaste råvaran i papperstillverkning är pappersmassa. Massan innehåller (ved)fibrer men också finmaterial och andra typers (ved)celler, så som kärlceller. Hur dessa komponenter beter sig under arkformationen i pappersmaskinen eller hur de bidrar till egenskaperna hos det färdiga pappret avgörs till stor del av massakomponenternas ytkemiska sammansättning, fysiska struktur och mängden joniserbara grupper på ytan. I denna avhandling studerades ytegenskaperna hos fraktionerade kemiska massor och returfibermassor med avancerade analystekniker. Rester av avfärgningskemikalier identifierades på både returfibrer och på kärlceller. Dessa kan påverka arkformationen och arkstyrkan på returfiberpapper. Kärlcellernas cellväggsstruktur visade sig skilja sig från fibrernas. Resultaten kan främja utvecklingen av returfiberprosessen och användningen av kärlcellsrika lövvedsmassor.

Carbon footprint of the colombian cocoa production

ABSTRACT Cocoa is an important commercial crop in the tropics; and estimating the carbon emissions in the producing-areas is a worthwhile effort. The main goal of the current paper was to evaluate the carbon footprint (CF) per kilogram of Colombian cocoa bean produced under conventional and agroforestry managements, following the methods proposed by PAS 2050. In this research, we compared our results to other worldwide researches, showing an overview of the current limitations and challenges involving the CF researches. Our results showed that all calculated environmental burdens were lower for the conventional management. In the agroforestry practice, composting of cocoa pod husks contributed with approximately 34.00E+00 g methane and 2.55E+00 g nitrous oxide emissions per kilogram of cocoa grain produced. Therefore, such practice could reduce CF by 6.00E+00 kg CO2 Eq kg-1, which is certainly a significant amount. These cocoa residues left on the ground have a strong impact on CF of both studied managements due to the anaerobic decomposition of organic matter, which represents more than 85% of emissions. We concluded that both evaluated production processes can emit environmental burdens at the same magnitude. Definitely, there is a widespread need to improve cocoa production system by changing old and less productive plants to the so called clones to ensure cocoa yield and quality worldwide.