Growing concerns about climate change and the inevitable depletion of fossil fuel resources have led to an increased focus on renewable energy technologies and reducing GHG emissions. Limiting the atmospheric level of CO2 is essential to prevent the most damaging effects of climate change. Among renewable energy resources, biomass combustion has the largest potential to contribute to global energy demands, however it is considered to be a carbon neutral solution and so only limits CO2 concentrations rather than reducing them. Through pyrolysis rather than combustion, biomass can lead to carbon negative liquid, gaseous and solid fuels while also offering a route for long term carbon storage in the form of biochar. Biochar is a carbonaceous material which has shown potential for improving soil fertility, reducing GHG emissions and most importantly long term C storage in the environment. However many questions still remain unanswered with regard to biochar, especially the influence that process conditions can have on its performance in soil as well as any potential trade-offs between soil amendment, C sequestration and heat/power generation. This thesis is therefore focused on assessing the influence that process conditions and feedstock selection have on biochar properties related to carbon stabilisation, improving soil fertility (functional properties) as well as the distribution of energy amongst the pyrolysis co-products. To achieve this, a systematic set of biochar samples was produced, using a wide range of pyrolysis parameters (highest treatment temperature (HTT), heating rate, residence time, carrier gas flow rate and feedstock type), and analysed for physicochemical and functional properties. Pyrolysis HTT consistently showed a dominant influence on determining the final yields and properties of biochar, while the effect of other production parameters was varied. In this thesis the candidate first studied the effect that process conditions had on the long term stability of biochar, as an important indicator of its ability to sequester carbon. While increasing the HTT resulted in a decrease in biochar yield, overall the yield of stable-C increased with temperature. This meant that by applying a higher HTT during pyrolysis a higher C sequestration potential for biochar was achieved. Next to be examined was the influence that process conditions had on other functional properties (labile-C yield, biochar pH, extractable nutrients and cation exchange capacity (CEC)) was then examined. The labile-C yield of biochar decreased with increasing HTT due to the release of volatile matter, while the CEC and concentration of extractable nutrients tended to be higher in biochar produced at 450oC rather than greater HTTs. Biochar pH was also highly alkaline at elevated HTT. This indicated that while high HTT favoured C sequestration and biochar pH, lower HTT may be more favourable for other functional properties. Furthermore by assessing the mass and energy distribution amongst the solid, liquid and gaseous fractions, it was possible to determine the energy balance of the process and through this evaluate the trade-off between the C sequestration potential of biochar and the energy output of the liquid and gas fractions. As the severity of pyrolysis was raised, the total energy stored within the liquid and gaseous co-products increased at the expense of the energy content of biochar, therefore increasing the available energy output of the system and reducing the energy lost when using biochar for carbon storage rather than for bioenergy. This also demonstrated that the pyrolysis process could be fine-tuned to increase the amount of stored C while also improving the heat/power generation of the system. The higher energy content of the gas stream at elevated HTT was also seen to contain sufficient energy to sustain the pyrolysis process, which would free up the solid and liquid fractions for higher value applications while reducing the necessity for external fuel sources. Finally, the data set was used to produce statistical models enabling the prediction of biochar stable-C yield as well as the heating value of biochar. The results of this thesis therefore demonstrate that through applying high HTT the potential energy output of the pyrolysis system can be increased while producing a biochar product with high C sequestration potential and positive functional properties for soil amendment. Due to potential trade-offs, the final choice of process conditions and feedstock would then be made based on the specific requirements of a selected site for biochar application. Understanding the influence that production conditions have on the functional properties of biochar as well as the energy balance of the system is critical to developing specifically engineered bespoke biochar, be it for agricultural use, carbon storage, energy generation or combinations of the three.

Thesis (MScAgric)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Biochar (charcoal) is lauded by many scientists as an effective way to remove carbon dioxide from the atmosphere and storing it in a very stable form in the soil for hundreds to thousands of years, whilst promoting soil fertility and productivity. Considering that no significant amounts of charcoal are presently accumulating in the environment, despite considerable amounts produced globally in natural and man-made fires, this study focuses on understanding the degradation of biochar and its interactions with plants and soil organisms. The following experiments were conducted to achieve this goal. Controlled chemical oxidation of biochar, using different concentrations of hydrogen peroxide, was conducted in an attempt to mimic the enzymatic degradation of biochar by basidiomycetes. The changes occurring in biochars structure and chemistry were assessed afterwards. Furthermore, aerobic and anaerobic digestion of biochar was conducted in vitro, and in vivo to investigate the changes occurring in biochar‘s elemental composition and chemistry during oxidation and factors that play a determining role in the rate of biochar degradation. The influence of biochar in soil on free-living and symbiotic microbial communities as well as its impact on total plant biomass production and root development was assessed in three greenhouse pot trials using wheat and green beans as test plants It was proven that biochar is almost fully H2O2-degradable, mostly through hydroxylation and carboxylation reactions which led to the formation of various short chained carboxylic acids, surface saturation with acidic functional groups as determined by the surface acidity measurements and proven by the increase in the intensity of FT-IR peaks associated with carboxyl and phenolic C-O groups. Furthermore, hydrogen peroxide treatment resulted in preferential removal of volatile organic carbons and led to the purification of biochar as evident by the new, more intense and sharper peaks in the region of 1600-1000 cm-1. These FT-IR peaks are considered as the more recalcitrant fraction of biochar and were shown to be mostly associated with transformation products of lignin and cellulose formed during pyrolysis. The incubation trial confirmed that biochar cannot be utilized as a sole carbon source without the addition of nutrients or glucose, to activate microbial activity within the columns. Furthermore, abiotic oxidation can be facilitated by oxidative soil minerals such as birnessite, but oxidation with atmospheric oxygen did not result in the evolution of CO2 from biochar. The average CO2 production in pot trials without plants in both the fertilized and unfertilized treatments increased linearly (R2= 0.80; 0.79 respectively) with increasing biochar application rates when biochar was the main carbon sources. Anaerobic degradation of biochar by a methanogenic consortium was much more efficient in utilizing biochar as a carbon source, compared to aerobic digestion. The anaerobic digesters maintained a chemical oxygen demand (COD) removal efficiency of 30% per week with continuous production of CO2, whilst methane production was very erratic. We proposed that better control over pH and alkalinity as well as an increase in hydraulic retention time would improve both the COD removal efficiency and methane production. Field incubations resulted in various degrees of oxidation at different incubation sites. An increase in the oxygen content and a decreased in the carbon content of biochar‘s elemental composition and also an increase in the surface acidity due to a larger amount of carboxyl acid groups on the surface as seen in the increase in the FT-IR peak at 1700 cm-1 confirmed that biochar are susceptible to oxidation under field conditions. We came to the conclusion that oxidation and mineralization of biochar in this trial occurred at a faster rate in soils with a higher microbial activity. The pot trials, confirmed that biochar does not serve as a fertilizer even though it did increase total biomass production between biochar application rates of 0.05-2.5 % (w/w). For agricultural purposes the addition of biochar should always be applied together with NPK fertilizer. In both the wheat and green bean trials it was confirmed that biochar application rates of 0.05-0.5% (w/w) on the sandy, slightly acidic soil used in this trial resulted in the greatest biomass production and fertilizer use efficiency. Biochar additions resulted in considerable increases in soil pH and C/N ratios which were considered as the main reasons for the decrease in microbial biomass in the unfertilized green bean treatments as it made the uptake of N more limited. The addition of fertilizer however, alleviated N-supply constraints and as a result promoted microbial growth at all biochar application rates of pot trial 1. However, biochar did not promote mycorrhyzal colonization and caused a decrease in the mycorrhizal colonization of roots with increasing biochar application rates and within biochar layers. Biological nitrogen fixation, however, reacted positively to the addition of biochar. High biochar application rates significantly enhanced the plants reliance on these symbiotic relationships. We hypothesized that biochar physically immobilized N into its microvoids through capillary suction and then served as a physical barrier between plant roots and absorbed N. However, immobilzation of N by microbes could also have contributed to the decrease in N uptake if one takes into account that microbial activity was higher (respiration data) at the higher biochar application rates. Further investigations are needed to warrant this hypothesizes. / AFRIKAANSE OPSOMMING: Biochar (houtskool) is deur talle wetenskaplikes die lof toegeswaai as ‘n doeltreffende manier om koolstofdioksied uit die atmosfeer te verwyder en in ‘n baie stabiele vorm in die grond vir honderde tot duisende jare te stoor, terwyl dit die grondvrugbaarheid en produktiwiteit bevorder. As daar in ag geneem word dat geen beduidende hoeveelheid houtskool in die omgewing opgaar nie ondanks groot hoeveelhede wat wêreldwyd deur natuurlike en mensgemaakte brande gevorm word, is die doel van hierdie studie om die afbraak en die interaksie van biochar met plante en grondmikrobes beter te verstaan. Om hierdie doel te bereik is die volgende eksperimente uitgevoer: Beheerde chemiese oksidasie is op die biochar toegepas deur gebruik te maak van verskillende konsentrasies waterstofperoksied in 'n poging om die ensiematiese afbraak van biochar deur basidiomysete na te maak. Die veranderinge wat plaasvind in die struktuur en chemie van biochar is daarna bestudeer. Daarbenewens is die aerobiese and anearobiese afbraak van biochar toegepas beide in vitro- en in vivo-, om die veranderinge wat in biochar se elementele samestelling en chemie plaasvind gedurende oksidasie en ook die faktore wat 'n bepalende rol in die tempo waarteen biochar afbreek, te ondersoek. Die invloed van biochar in die grond op vrylewende en simbiotiese mikrobiese populasies, sowel as die impak daarvan op die totale plant biomassa produksie en ontwikkeling van plantwortels, is vasgestel tydens drie groeitonnel potproewe waarby koring en boontjies as planttoetsspesies gebruik is Dit is bewys dat biochar byna volledig deur H2O2 afgebreek kan word, meestal deur hidroksilasie en karboksilasie reaksies wat gelei het tot die vorming van 'n verskeidenheid kort ketting karboksielsure, 'n biochar oppervlak versadig met suurvormende funksionele groepe soos bepaal en bewys deur die toename in intensiteit van die FT-IR (Fourier Transvorm Infrarooi Spektroskopie) pieke geassosieer met karboksiel en fenoliese C-O groepe. Die behandeling van biochar met H2O2 het by voorkeur die vlugtige organise koolstof verwyder wat gelei het tot suiwering van die biochar, wat bevestig is deur die nuwe, meer intens en skerper FT-IR pieke in die area tussen 1600-1000 cm-1. Die FT-IR pieke word beskou as die meer weerstandbiedende fraksie van biochar en daar is bewys dat die pieke meestal met getransformeerde produkte van lignien en sellulose wat tydens pirolise gevorm is, geassosieer word. Die inkubasie proef het bevestig dat biochar nie deur mikrobes benut kan word as enigste bron van koolstof sonder die byvoeging van nutriente of glukose nie, om die mikrobes binne die inkubasie kolom te aktiveer. Daarbenewens kan abiotiese oksidasie van biochar deur oksidatiewe grondminerale soos birnessite (δ-MnO2) gefasiliteer word, terwyl oksidasie van biochar deur atmosferiese suurstof nie tot enige CO2 produksie gelei het nie. Nogtans het die gemiddelde CO2 produksie in die boontjie potproef, sonder die plante, in beide die onbemeste en bemeste behandelings linieer toegeneem (R2= 0.80; 0.79 onderskeidelik) met toenemende aanwendingskoers van biochar, toe biochar die dominante bron van koolstof was. Anaerobiese afbraak van biochar deur 'n metanogeniese konsortium was heelwat meer effektief in die benutting van biochar as enigste koolstofbron in vergelyking met aerobiese afbraak. Die anaerobiese verteertoestel het konstant 30% van die chemiese suurstof behoefte (CSB) weekliks verwyder, gepaardegaande met die voortdurende produksie van CO2, terwyl metaangasproduksie baie onegalig was. Dit word voorgestel dat met beter beheer oor pH en alkaliniteit en ook 'n langer hidrouliese retensie tyd, kan beide die CSB verwyderingseffektiwiteit en metaangasproduksie verbeter kan word. Veld inkubasies het verskeie mates van oksidasie meegebring tussen die verskillende inkubasie liggings. 'n Toename in die suurstofinhoud en 'n afname in die koolstof inhoud van biochar se elementele samestelling sowel as 'n toename in die oppervlak suurheid weens die groter hoeveelheid karboksielsure aan die oppervlak soos blyk uit die FT-IR piek by 1700 cm-1, het bevestig dat biochar wel vatbaar is vir oksidasie onder veld kondisies. Die gevolgtrekking was dat biochar oksidasie en mineralisasie in hierdie proef teen 'n vinniger tempo plaasgevind het in die gronde met hoer mikrobiese aktiwiteit. Die potproewe het bevestig dat biochar nie as bemestingsstof sal dien nie, alhoewel dit tot 'n toename in die biomassa produksie gelei het tussen die biochar aanwendingskoerse van 0.05-2.5% (w/w). Vir landbou doeleindes moet die aanwending van biochar altyd gepaardgaan met NPK bemesting. Beide die koring- en boontjie proewe het bevestig dat die biochar aanwendingskoerse tussen 0.05-0.5% (w/w) op die sanderig, effens suur grond wat gebruik is in die proef, gelei het tot die hoogste biomassa produksie en bemestingseffektiwiteit. Die toediening van biochar het gelei tot merkbare toenames in grond pH en C/N verhoudings en hierdie toestande was beskou as die hoof redes vir die afname in mikrobiese biomassa in die onbemeste boontjie behandelings omdat dit die opname van N meer beperk. Die toediening van bemesting het egter die beperkings op N voorsiening opgehef en as gevolg hiervan die mikrobiese biomassa bevorder by alle biochar aanwendingskoerse. Biochar het egter nie mikorrisa kolonisasie bevorder nie en het gelei tot =n afname in die mikorrisa kolonisasie van die wortels met toenemende biochar aanwendingskoerse en binne in die biochar lae van potproef 1. Biologiese stikstof vaslegging het egter positief reageer op die toediening van biochar. Hoë biochar aanwendingskoerse het beduidend die plant se afhanklikheid op hierdie simbiotiese verhouding verhoog. Ons hipotese is dat die biochar fisies N immobiliseer binne in die mikro-ruimtes deur kapillêre suigaksie en dan as 'n fisiese versperring dien tussen die plantwortels en die geabsorbeerde N. Die immobilisasie van minerale N deur mikrobes kon egter ook grootliks bygedra het tot die afname in N opname as daar in ag geneem word dat mikrobiese aktiwiteit (respirasie data) hoër was by die hoër biochar aanwendingskoerse. Verdere ondersoeke moet daarom uitgevoer word om hierdie hipotese te bevestig.

Orientador: Fábio Minoru Yamaji / Resumo: Os atuais padrões mundiais de consumo energético estão baseados na utilização de combustíveis fósseis, os quais, além de serem não renováveis, geram diversos problemas ambientais. Nos últimos anos houve um aumento na busca por fontes energéticas alternativas e mais sustentáveis, como as biomassas provenientes de resíduos agroindustriais, as quais podem apresentar grande potencial energético por área e baixos impactos ambientais. Com o intuito de minimizar os problemas ambientais relacionados à geração e descarte de resíduos provenientes das atividades de cultivo de cogumelos, esse estudo teve como objetivo avaliar o potencial bioenergético do resíduo de cultivo de shiitake (RCS) seco e por meio de sua conversão termoquímica pelo processo de pirólise em três temperaturas diferentes (350°C, 450°C e 550°C). Mediante às análises, o biocarvão de 350°C (BC350) foi considerado com o maior potencial energético devido à menor quantidade de cinzas e maiores quantidades de materiais voláteis, carbono fixo, poder calorífico, rendimento gravimétrico e fator de rendimento gravimétrico. As análises químicas e físicas revelaram que o RCS seco apresenta uma natureza bastante complexa, característica comumente encontrada em materiais de origem lignocelulósica. As análises termogravimétricas foram realizadas em três rampas de aquecimento, 10°C/min, 15°C/min e 20°C/min, em atmosfera oxidante e inerte. Foram identificadas etapas de conversão referentes à perda de água e degradação de hemicelulo... (Resumo completo, clicar acesso eletrônico abaixo) / Current global patterns of energy consumption are based on the use of fossil fuels, which are not only non-renewable resources, but also generate vast environmental problems. Recent years have witnessed an increasing search for alternative, more sustainable, energy sources, such as biomasses originated from agroindustrial residues, a material that may present great energetic potential per area and minor environmental impacts. Aiming at minimizing environmental impacts related with the generation and discard of mushroom cultivation residues, the present study intended to evaluate the bioenergetic potential of the spent shiitake substrate (SSS), both in its dry form and after its thermochemical conversion by a pyrolysis process in 3 different temperatures (350°C, 450°C e 550°C). Further analyses founded the consideration that the 350°C biochar (BC350) was that with the greatest energetic potential, due to its reduced ash amounts and higher volatile amounts, fixed carbon, heat value, gravimetric yield and gravimetric yield factor. Chemical and physical analyses revealed that the dry SSS possesses a highly complex nature, characteristics commonly found in lignocellulosic materials. Thermogravimetric analyses were performed in 3 heating rates, 10°C/min, 15°C/min and 20°C/min in oxidizing and inert atmospheres. Conversion steps related with water loss and degradation of hemicellulose, cellulose and lignin have been identified. The kinetic study was carried out by non-isothermal and non-isoconversional Kissinger method. The activation energies obtained were of 110.3 kJ mol-1 and 136 kJ mol-1 for the SSS and BC350, respectively and are within the range found for other biomasses. The SSS presented features that allow the conclusion that such residue possesses great potential for bioenergy generation applications, potential which may be improved by means ... (Complete abstract click electronic acess below) / Mestre

Orientador: André Henrique Rosa / Resumo: Biochar é produzido pela pirólise de resíduos de diferentes biomassas, podendo ser uma alternativa interessante para obtenção de um adsorvente para remoção de íons metálicos e metaloides em aguas naturais. O objetivo deste trabalho foi avaliar a eficiência de remoção de íons As(lll) por biochars normal (BN) e modificado quimicamente com íons Fe(III) (biochar magnético, BM), produzidos a partir da pirólise do bagaço de cana-de-açúcar e de palha de milho em 4 diferentes temperaturas (300, 400, 500 e 600°C). O pH de carga zero (pHpcz) das amostras de biochar ficou na faixa de 6, evidenciando que abaixo dessa faixa de pH a superfície do biochar está carregada positivamente. Resultados de FT-IR demonstrou que o aumento da temperatura leva a diminuição dos grupos funcionais ácido e no caso do MEV demostrou que, conforme de aumenta a temperatura, se percebe aumento do tamanho e volume dos poros dos biochars. Para analisar a eficiência e o comportamento de adsorção foram feitos experimentos em batelada, para verificação da cinética e isotermas de adsorção. Os resultados obtidos evidenciaram que para o biochar normal em ambos casos (bagaço de cana de açúcar e palha de milho) a adsorção foi baixa. Já ótimo desempenho foi observado pelos biochars magnéticos em todas as condições de pH estudados (4, 5 e 6), atingindo equilíbrio de adsorção de 95% em cerca de 10 minutos. Em relação a isoterma de adsorção os dados foram analisados com os modelos de Langmuir e Freundlich, ajustando-se melho... (Resumo completo, clicar acesso eletrônico abaixo) / Biochar is produced by the pyrolysis of residues from different biomasses, and may be an interesting alternative to obtain an adsorbent for the removal of metal ions and metalloids in natural waters. The objective of this work was to evaluate the efficiency of removal of As (III) ions by normal biochars (BN) and chemically modified with Fe (III) ions (magnetic biochar, BM), produced from pyrolysis of sugarcane bagasse sugar and corn straw at 4 different temperatures (300, 400, 500 and 600 ° C). The zero charge pH (pHpcz) of the biochar samples was in the range of 6, showing that below this pH range the surface of the biochar is positively charged. Results of FT-IR showed that the increase in temperature leads to a decrease in the acid functional groups and in the case of MEV it was shown that, as the temperature increases, an increase in the size and volume of the pores of the biochars is observed. In order to analyze the adsorption efficiency and behavior, batch experiments were carried out to verify kinetics and adsorption isotherms. The results showed that for the normal biochar in both cases (sugar cane bagasse and corn straw) the adsorption was low. Already excellent performance was observed by the magnetic biochars in all pH conditions studied (4, 5 and 6), reaching a 95% adsorption equilibrium in about 10 minutes. In relation to the adsorption isotherm the data were analyzed with the Langmuir and Freundlich models, adjusting better to Langmuir with a R2≈1 for BM of corn straw and R2≈0.8999 for BM of sugarcane bagasse. sugar, indicating in both cases chemical adsorption. The results obtained in this work indicate that the use of sugarcane bagasse residues and corn straw to produce biochar from pyrolysis in the presence of Fe (III) ions may lead to the production of an adsorbent of low cost and high efficiency... (Complete abstract electronic access below) / Mestre

Orientador: André Henrique Rosa / Resumo: Todo produto agrícola interfere na situação termodinâmica de solos, afetando as interações entre solo-microorganismos-plantas. Biochar é definido como um material carbonáceo multifuncional que atua como condicionante/ fertilizante e eleva a qualidade de solos. Pode estar presente naturalmente em solos férteis ou produzido a partir da pirólise de resíduos agrícolas gerando produtos de maior valor agregado. A literatura destaca casos de sucesso de sua aplicação no solo e como material adsorvente de contaminantes orgânicos e inorgânicos. No entanto, poucas informações estão disponíveis sobre possíveis efeitos antagônicos do biochar aos microorganismos do solo e alterações diretas no desenvolvimento de plântulas. Visando entender interações do biochar no sistema solo-microorganismos-plantas, este trabalho objetivou identificar os efeitos de diferentes doses de biochar produzidos a partir de bagaço de cana-de-açúcar e palha de sabugo de milho na interação com nutrientes, desenvolvimento de fungos ligninolíticos, bactérias promotoras do crescimento de plantas e de plântulas de milho. Para tanto, as amostras de biochar foram produzidas por meio de pirólise em nove regimes de temperatura para compreender quais mudanças morfológicas e físico-químicas ocorrem na formação do biochar. Com o objetivo de preservar as interações multitróficas do solo, foram explorados os efeitos de diferentes doses de biochar no crescimento radial de micélios três diferentes espécies de fungos ligninolítico... (Resumo completo, clicar acesso eletrônico abaixo) / Any agricultural product that reaches the pedological system interferes in the thermodynamic situation of soil non-equilibrium, affecting the soil-microorganisms-plants set. In recent years, biochar has been identified as a conditioning / fertilizing material that helps raise the soil qualities. Biochar is a multifunctional carbonaceous material already existing naturally in fertile soils. However, the non-natural production of biochar has been considered as an alternative destination to agricultural waste that generates value-added products. The literature highlights successful cases of its application in the soil and as adsorbent material of organic and inorganic contaminants. However, little information is available on possible antagonistic effects of biochar on soil microorganisms and direct changes in seedling development. In order to understand possible points of bifurcations that biochar can generate in the soil-microorganisms-plants system, this work aimed to identify the effects of different doses of biochar produced from sugarcane bagasse and corn cob in the growth and development of ligninolytic fungi, plant growth promoting bacteria and maize seedlings. For this, the biochar samples were produced by means of pyrolysis in nine temperature regimes to understand which morphological and physicochemical changes occur in the formation of biochar. With the objective of preserving the soil multitrophic interactions, it was explored the effects of different doses of biochar on the radial growth of mycelium three different species of ligninolytic fungi: Bjerkandera adusta, Pleurotos ostreaus and Trametes versicolor. A species-dependent effect was found where the same biochar samples can cause acute toxicity and additive effect on the growth of these fungi... (Complete abstract electronic access below) / Doutor

Organic wheat grown under dryland conditions encounters challenges such as limited nutrients and water. Maintaining organic wheat production requires solutions to these problems in order to retain economic sustainability for the farmers. Research on biochar and compost have been conducted globally. Despite well known benefits of compost on soil and crop production, few organic farmers apply compost to their fields. Research on biochar is still new. Biochar is charcoal created from pyrolyzing agricultural material under conditions of low oxygen and high heat. Many studies claim that biochar is a valuable soil amendment for improving organic production and reducing environmental pollution (such as greenhouse gas emission, water pollution, or nutrient leaching). It may hold more moisture in the soil and retain nutrients. We conducted a study on the interactions between biochar and compost in organic winter wheat production and soil quality under dryland conditions. We analyzed the response to biochar and compost, and investigated individual and combined effects on wheat yield, wheat quality, and soil quality. This study revealed that compost had significant impacts on increasing wheat yield and had slight impacts on soil quality while biochar had none to slight impacts on soil and wheat production. We validated the usefulness of compost for organic wheat production in dryland condition, but found no real benefit for biochar in this first year.

Hydrogen sulphide is an environmentally hazardous gas which is present in many gas streams associated with oil and gas industry. Oxidation of H2S to sulphur in air produces no bulky or waste material and requires no further purification. Activated carbon is known as a catalyst for this reaction.<p> In this research, a coal-based precursor (luscar char) and a biomass-based precursor (biochar) were used for production of activated carbons by two common methods of activation: physical and chemical activation in which steam and potassium hydroxide (KOH), respectively, were used. Experiments were designed by the statistical central composite design method. Two models were developed for the BET surface area and reaction yield of each activation process. These models showed the effects of operating conditions, such as activation temperature, mass ratio of activating agent to precursor, activation time, and nitrogen flowrate on the BET surface area and reaction yield for each activation method for each precursor. The optimum operating conditions were calculated using these models to produce activated carbons with relatively large BET surface area (> 500 m2/g) and high reaction yield (> 50 wt %). The BET surface area and reaction yield for activated carbons produced at optimum operating conditions showed maximum 7 and 7.4 % difference, respectively, comparing to the values predicted by models.<p> The activated carbons produced at optimum operating conditions were used as the base catalysts for the direct oxidation of 1 mol % hydrogen sulphide in nitrogen to sulphur at the temperature range of 160-205 oC and pressure of 700 kPa. Originally activated carbons showed a good potential for oxidation of hydrogen sulphide by their selectivity for sulphur product and low amount of sulphur dioxide production. To improve the performance of steam-activated carbons, the catalysts were modified by acid-treatment followed by thermal desorption. This method increased the break-through times for coal-based and biomass-based catalysts to 115 and 141 minutes, respectively. The average amounts of sulphur dioxide produced during the reaction time were 0.14 and 0.03 % (as % of hydrogen sulphide fed to the reactor) for modified activated carbons prepared from biochar and luscar char, respectively. The effects of porous structure, surface chemistry, and ash content on the performances of these activated carbon catalysts were investigated for the direct oxidation reaction of hydrogen sulphide.<p> The acid-treatment followed by thermal desorption of activated carbons developed the porosity which produced more surface area for active sites and in addition, provided more space for sulphur product storage resulting in higher life time for catalyst. Boehm titration and temperature program desorption showed that the modification method increased basic character of carbon surface after thermal desorption in comparison to acid-treated sample. In addition, the effects of impregnating agents (potassium iodide and manganese nitrate) and two solvents for impregnation process were studied on the performance of the activated carbon catalysts for the direct oxidation of H2S to sulphur.<p> Sulphur L-edge X-ray near edge structure (XANES) showed that the elemental sulphur was the dominant sulphur species in the product. The kinetic study for oxidation reaction of H2S over LusAC-O-D(650) was performed for temperature range of 160-190 oC, oxygen to hydrogen sulphide molar ratio of 1-3, and H2S concentration of 6000-10000 ppm at 200 kPa. The values of activation energy were 26.6 and 29.3 kJ.gmol-1 for Eley-Rideal and Langmuir-Hinshelwood mechanisms, respectively.

Loss of soil organic carbon (SOC) resulting from intensive agriculture practices has impacts on both climate change, through emissions of greenhouse gases, as well as food security because of declines in soil fertility. A possible solution for rapidly restoring and stabilizing SOC is through additions of biochar to soil. Biochar is a carbon-rich material formed by pyrolysis (heating) of biomass in an oxygen-limited environment. A biofuel company, ABRI-Tech, has proposed an economically feasible method of using biochar in Canadian agriculture that involves enriching biochar with urea ammonium nitrate (UAN) fertilizer and applying small amounts (~1 t/ha) of biochar annually. The main objectives of this study were to evaluate the ability of biochar-UAN (Char+) to increase agricultural productivity and SOC in temperate regions. This study presents the results of a growth chamber experiment, two field trials and Century Soil Organic Matter modeling. In the growth chamber experiment, Char+ significantly increased the shoot dry mass (DM) of maize (Zea mays) by 310% in sandy textured soil, 112% in medium soil and no significant difference was observed in fine soil. However, in all soil textures, as well as the Char+ field trial, the maize DM resulting from 1 t/ha Char+ was not significantly different from UAN treatments. The biochar field trials demonstrated that if 1 t/ha of Char+ was applied annually the maize biomass production would not be affected after 6-12 years (6.2-12.4 t biochar/ha), and there may be slight improvement in yields of about 25% after 25 years (24.8 t biochar/ha). Although no significant differences in SOC were found in the field trial, there was a trend of increasing SOC as biochar application rates increased. The Century model predicted that annual addition of 1 or 2 t Char+/ha will increase SOC more than other management practices, including crop rotation, no-till and manure, over a 150 year period. The model predicted that applying 1 t Char+/ha per year to a sandy soil will increase SOC by 10% after 10 years and 17% after 20 years. This research is significant because it shows how an economically feasible method of using biochar can improve the sustainability of agroecosystems and increase terrestrial carbon sequestration in temperate regions.

Hydrogen sulphide is an environmentally hazardous gas which is present in many gas streams associated with oil and gas industry. Oxidation of H2S to sulphur in air produces no bulky or waste material and requires no further purification. Activated carbon is known as a catalyst for this reaction.<p> In this research, a coal-based precursor (luscar char) and a biomass-based precursor (biochar) were used for production of activated carbons by two common methods of activation: physical and chemical activation in which steam and potassium hydroxide (KOH), respectively, were used. Experiments were designed by the statistical central composite design method. Two models were developed for the BET surface area and reaction yield of each activation process. These models showed the effects of operating conditions, such as activation temperature, mass ratio of activating agent to precursor, activation time, and nitrogen flowrate on the BET surface area and reaction yield for each activation method for each precursor. The optimum operating conditions were calculated using these models to produce activated carbons with relatively large BET surface area (> 500 m2/g) and high reaction yield (> 50 wt %). The BET surface area and reaction yield for activated carbons produced at optimum operating conditions showed maximum 7 and 7.4 % difference, respectively, comparing to the values predicted by models.<p> The activated carbons produced at optimum operating conditions were used as the base catalysts for the direct oxidation of 1 mol % hydrogen sulphide in nitrogen to sulphur at the temperature range of 160-205 oC and pressure of 700 kPa. Originally activated carbons showed a good potential for oxidation of hydrogen sulphide by their selectivity for sulphur product and low amount of sulphur dioxide production. To improve the performance of steam-activated carbons, the catalysts were modified by acid-treatment followed by thermal desorption. This method increased the break-through times for coal-based and biomass-based catalysts to 115 and 141 minutes, respectively. The average amounts of sulphur dioxide produced during the reaction time were 0.14 and 0.03 % (as % of hydrogen sulphide fed to the reactor) for modified activated carbons prepared from biochar and luscar char, respectively. The effects of porous structure, surface chemistry, and ash content on the performances of these activated carbon catalysts were investigated for the direct oxidation reaction of hydrogen sulphide.<p> The acid-treatment followed by thermal desorption of activated carbons developed the porosity which produced more surface area for active sites and in addition, provided more space for sulphur product storage resulting in higher life time for catalyst. Boehm titration and temperature program desorption showed that the modification method increased basic character of carbon surface after thermal desorption in comparison to acid-treated sample. In addition, the effects of impregnating agents (potassium iodide and manganese nitrate) and two solvents for impregnation process were studied on the performance of the activated carbon catalysts for the direct oxidation of H2S to sulphur.<p> Sulphur L-edge X-ray near edge structure (XANES) showed that the elemental sulphur was the dominant sulphur species in the product. The kinetic study for oxidation reaction of H2S over LusAC-O-D(650) was performed for temperature range of 160-190 oC, oxygen to hydrogen sulphide molar ratio of 1-3, and H2S concentration of 6000-10000 ppm at 200 kPa. The values of activation energy were 26.6 and 29.3 kJ.gmol-1 for Eley-Rideal and Langmuir-Hinshelwood mechanisms, respectively.

Bioresources are generated in a variety of environments and each presents unique risks and benefits associated with land application. Bioresources from livestock, urban and bioenergy systems were selected and evaluated through field, greenhouse and laboratory studies of potential risk and benefits of recycling to agricultural and urban landscapes. The waste stream, including feedstock sources and treatment processes, affects composition and properties of bioresources and effects on biogeochemical cycles of amended soils. Variation of decomposition and nutrient mineralization rates among bioresources used to amend soil for turfgrass and forage reflected variation among contrasting feedstock sources and treatments prior to application. During turfgrass establishment, plant available nitrogen and nitrogen mineralized from a bioresource from livestock waste streams, (Geotube! residual solids, supplied N in excess of crop uptake potential and contributed to leaching loss of N. In contrast, N mineralization rates from bioresources generated during methane production from dairy manure (manure solids) were not sufficient to maximize crop production, necessitating N fertilizer application. In addition to variation of composition, bioresource effects on crop productivity and environmental quality vary among management practices and between forage and turfgrass cropping systems. Large application rates of bioresources increase soil nutrient concentration and potential crop productivity, but contribute to increased nutrient loss in drainage and surface runoff. Yet, incorporation or Alum treatment of bioresources will reduce runoff loss of dissolved P and protect water quality without sacrificing crop productivity. Alum treatment of bioresources prior to land application effectively reduced runoff loss of dissolved P to levels observed for control soil. For situations in which large, volume-based bioresource rates are top-dressed or incorporated, export of applied nutrients environmental impacts were compared between forage and turfgrass systems. Starting during the initial year of production, annual export of applied N and P in Tifway bermudagrass sod was greater than export through forage harvests of Tifton 85. Low forage yield limited N and P export from Tifton 85 during the year of establishment, but increased forage yield during the second year increased export of manure N and P to levels more comparable to sod. As variation between compost sources, turfgrass and forage production systems, and application methods indicated, effective management of bioresources is necessary to balance benefits and risk in cropping systems. Integrated assessment of bioresource composition and crop-specific management of application method and rate will enable sustainable bioresource cycling and crop productivity.