Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

The Ratios of Carbon, Nitrogen, and Phosphorus in a Wetland Coastal Ecosystem of Southern India

The fertility of the coastal and estuarine waters is of great concern because of its influence on the productivity of these waters. Seasonal variations in the distribution of organic carbon, total nitrogen and total phosphorus in the sediments of Kuttanad Waters, a part of the tropical Cochin Estuary on the south west coast of India, are examined to identify the contribution of sediments to the fertility of the aquatic systems. The adjoining region has considerable agricultural activity. The fresh water zones had higher quantities of silt and clay whereas the estuarine zone was more sandy. Organic carbon, total phosphorus and total nitrogen were higher in the fresh water zones and lower in the estuarine zones. Total phosphorus and organic carbon showed the lowest values during monsoon periods. No significant trends were observed in the seasonal distributions of total nitrogen. Ratios of C/N, C/P and N/P, and the phosphorus and nitrogen content indicate significant modification in the character of the organic matter. Substantial amounts of the organic matter can contribute to reducing conditions and modify diagenetic processes

Nitrogen and carbon dynamics in grassland soils and plants after application of digestate

A better understanding of effects after digestate application on plant community, soil microbial community as well as nutrient and carbon dynamics is crucial for a sustainable grassland management and the prevention of species and functional diversity loss. The specific research objectives of the thesis were: (i) to investigate effects after digestate application on grass species and soil microbial community, especially focussing on nitrogen dynamic in the plant-soil system and to examine the suitability of the digestate from the “integrated generation of solid fuel and biogas from biomass” (IFBB) system as fertilizer (Chapter 3). (ii) to investigate the relationship between plant community and functionality of soil microbial community of extensively managed meadows, taking into account temporal variations during the vegetation period and abiotic soil conditions (Chapter 4). (iii) to investigate the suitability of IFBB-concept implementation as grassland conservation measure for meadows and possible associated effects of IFBB digestate application on plant and soil microbial community as well as soil microbial substrate utilization and catabolic evenness (Chapter 5). Taken together the results indicate that the digestate generated during the IFBB process stands out from digestates of conventional whole crop digestion on the basis of higher nitrogen use efficiency and that it is useful for increasing harvestable biomass and the nitrogen content of the biomass, especially of L. perenne, which is a common species of intensively used grasslands. Further, a medium application rate of IFBB digestate (50% of nitrogen removed with harvested biomass, corresponding to 30 50 kg N ha-1 a-1) may be a possibility for conservation management of different meadows without changing the functional above- and belowground characteristic of the grasslands, thereby offering an ecologically worthwhile alternative to mulching. Overall, the soil microbial biomass and catabolic performance under planted soil was marginally affected by digestate application but rather by soil properties and partly by grassland species and legume occurrence. The investigated extensively managed meadows revealed a high soil catabolic evenness, which was resilient to medium IFBB application rate after a three-year period of application.

Ecological specificity of arbuscular mycorrhizae: evidence from foliar- and seed-feeding insects

Arbuscular mycorrhizal (AM) fungi have a variety of effects on foliar-feeding insects, with the majority of these being positive, although reports of negative and null effects also exist. Virtually all previous experiments have used mobile insects confined in cages and have studied the effects of one, or at most two, species of mycorrhizae on one species of insect. The purpose of this study was to introduce a greater level of realism into insect-mycorrhizal experiments, by studying the responses of different insect feeding guilds to a variety of AM fungi. We conducted two experiments involving three species of relatively immobile insects (a leaf-mining and two seed-feeding flies) reared in natural conditions on a host (Leucanthemum vulgare). In a field study, natural levels of AM colonization were reduced, while in a phytometer trial, we experimentally colonized host plants with all possible combinations of three known mycorrhizal associates of L. vulgare. In general, AM fungi increased the stature (height and leaf number) and nitrogen content of plants. However, these effects changed through the season and were,dependent on the identity of the fungi in the root system. AM fungi increased host acceptance of all three insects and larval performance of the leaf miner, but these effects were also season- and AM species-dependent. We suggest that the mycorrhizal effect on the performance of the leaf miner is due to fungal-induced changes in host-plant nitrogen content, detected by the adult fly. However, variability in the effect was apparent, because not all AM species increased plant N content. Meanwhile, positive effects of mycorrhizae were found on flower number and flower size, and these appeared to result in enhanced infestation levels by the seed-feeding insects. The results show that AM fungi exhibit ecological specificity, in that different. species have different effects on host-plant growth and chemistry and the performance of foliar-feeding insects. Future studies need to conduct experiments that use ecologically realistic combinations of plants and fungi and allow insects to be reared in natural conditions.

QTLs for shelf life in lettuce co-locate with those for leaf biophysical properties but not with those for leaf developmental traits

Developmental and biophysical leaf characteristics that influence post-harvest shelf life in lettuce, an important leafy crop, have been examined. The traits were studied using 60 informative F-9 recombinant inbed lines (RILs) derived from a cross between cultivated lettuce (Lactuca sativa cv. Salinas) and wild lettuce (L. serriola acc. UC96US23). Quantitative trait loci (QTLs) for shelf life co-located most closely with those for leaf biophysical properties such as plasticity, elasticity, and breakstrength, suggesting that these are appropriate targets for molecular breeding for improved shelf life. Significant correlations were found between shelf life and leaf size, leaf weight, leaf chlorophyll content, leaf stomatal index, and epidermal cell number per leaf, indicating that these pre-harvest leaf development traits confer post-harvest properties. By studying the population in two contrasting environments in northern and southern Europe, the genotype by environment interaction effects of the QTLs relevant to leaf development and shelf life were assessed. In total, 107 QTLs, distributed on all nine linkage groups, were detected from the 29 traits. Only five QTLs were common in both environments. Several areas where many QTLs co-located (hotspots) on the genome were identified, with relatively little overlap between developmental hotspots and those relating to shelf life. However, QTLs for leaf biophysical properties (breakstrength, plasticity, and elasticity) and cell area correlated well with shelf life, confirming that the ideal ideotype lettuce should have small cells with strong cell walls. The identification of QTLs for leaf development, strength, and longevity will lead to a better understanding of processability at a genetic and cellular level, and allow the improvement of salad leaf quality through marker-assisted breeding.

Free atmospheric CO2 enrichment increased above ground biomass but did not affect symbiotic N2-fixation and soil carbon dynamics in a mixed deciduous stand in Wales

Through increases in net primary production (NPP), elevated CO2 is hypothesizes to increase the amount of plant litter entering the soil. The fate of this extra carbon on the forest floor or in mineral soil is currently not clear. Moreover, increased rates of NPP can be maintained only if forests can escape nitrogen limitation. In a Free atmospheric CO2 Enrichment (FACE) experiment near Bangor, Wales, 4 ambient CO2 and 4 FACE plots were planted with patches of Betula pendula, Alnus glutinosa and Fagus sylvatica on a former arable field. Four years after establishment, only a shallow L forest floor litter layer had formed due to intensive bioturbation. Total soil C and N contents increased irrespective of treatment and species as a result of afforestation. We could not detect an additional C sink in the soil, nor were soil C stabilization processes affected by FACE. We observed a decrease of leaf N content in Betula and Alnus under FACE, while the soil C/N ratio decreased regardless of CO2 treatment. The ratio of N taken up from the soil and by N2-fixation in Alnus was not affected by FACE. We infer that increased nitrogen use efficiency is the mechanism by which increased NPP is sustained under elevated CO2 at this site.

Simple measures of climate, soil properties and plant traits predict national scale grassland soil carbon stocks

1. Soil carbon (C) storage is a key ecosystem service. Soil C stocks play a vital role in soil fertility and climate regulation, but the factors that control these stocks at regional and national scales are unknown, particularly when their composition and stability are considered. As a result, their mapping relies on either unreliable proxy measures or laborious direct measurements. 2. Using data from an extensive national survey of English grasslands we show that surface soil (0-7cm) C stocks in size fractions of varying stability can be predicted at both regional and national scales from plant traits and simple measures of soil and climatic conditions. 3. Soil C stocks in the largest pool, of intermediate particle size (50-250 µm), were best explained by mean annual temperature (MAT), soil pH and soil moisture content. The second largest C pool, highly stable physically and biochemically protected particles (0.45-50 µm), was explained by soil pH and the community abundance weighted mean (CWM) leaf nitrogen (N) content, with the highest soil C stocks under N rich vegetation. The C stock in the small active fraction (250-4000 µm) was explained by a wide range of variables: MAT, mean annual precipitation, mean growing season length, soil pH and CWM specific leaf area; stocks were higher under vegetation with thick and/or dense leaves. 4. Testing the models describing these fractions against data from an independent English region indicated moderately strong correlation between predicted and actual values and no systematic bias, with the exception of the active fraction, for which predictions were inaccurate. 5. Synthesis and Applications: Validation indicates that readily available climate, soils and plant survey data can be effective in making local- to landscape-scale (1-100,000 km2) soil C stock predictions. Such predictions are a crucial component of effective management strategies to protect C stocks and enhance soil C sequestration.

Integração de características de planta, de dossel e de solo para maior eficiência da adubação nitrogenada em cobertura em milho

O milho é um das culturas mais exigentes em nitrogênio (N). A sua aplicação na dose e época correta pode aumentar a sua eficiência de uso, diminuindo custos e danos ambientais. Foram estudadas características de planta, de dossel e de solo, como indicadores da disponibilidade de N no sistema solo-planta para predição da necessidade deste nutriente em cobertura em milho. Foram conduzidos cinco experimentos a campo e dois em casa de vegetação, nas estações de crescimento de 2002/03 e 2003/04, na Estação Experimental Agronômica e na Faculdade de Agronomia da UFRGS, em Eldorado do Sul e em Porto Alegre-RS, Brasil, respectivamente, e dois experimentos a campo no ano de 2004 no Estern Cereal and Oilseed Research Center, em Ottawa-Ontário, Canadá. Foram avaliadas, em diferentes locais e situações de manejo, características de planta, de dossel e de solo, citando-se: teores de nitrato, amônio e N mineral no solo e na folha; massa seca e área foliar da folha e da planta, teor e acúmulo de N na folha e na planta; teor relativo de clorofila na folha, medido pelo clorofilômetro, reflectância do dossel, medido por dois tipos de radiômetros e fluorescência da folha, medida pelo fluorômetro. Além disso, foram avaliados o rendimento de grãos e seus componentes e parâmetros de eficiência técnica e econômica de uso de N. Dentre as características de planta, o teor relativo de clorofila na folha, e dentre os de solo, o teor de nitrato no solo, destacaram-se entre os demais avaliados. Foram determinados níveis críticos e doses ótimas de N, bem como estabelecidas curvas de calibração para dois níveis de manejo com base nestas características para monitoramento da lavoura. No que diz respeito às características de dossel estudadas, a reflectância apresentou melhores resultados que a fluorescência como indicador do nível de N no sistema solo-planta. Os estudos realizados mostraram que dentre as caracteríticas avaliadas, atualmente, o teor relativo de clorofila na folha tem o maior potencial para auxiliar na determinação da época mais adequada para aplicação de N em cobertura em milho.

Espaçamento, densidade populacional e adubação nitrogenada na cultura do milho

A distribuição espacial de plantas por área é um recurso para aumentar a produtividade. Para materiais de alta produtividade, são necessárias mais informações quanto à resposta à adubação nitrogenada. Assim, avaliou-se na cultura do milho a influência do espaçamento, da densidade populacional e de doses de nitrogênio no teor de nitrogênio nas folhas, estimativa do teor de clorofila, número de grãos por espiga, massa de 1.000 grãos, produtividade e teor de proteína nos grãos. O trabalho foi instalado no ano agrícola 2000/2001 e constou de tratamentos representados pela combinação de dois espaçamentos entre as linhas (0,80 e 0,60 m) com três densidades populacionais (40, 60 e 80.000 plantas ha-1) e quatro doses de nitrogênio em cobertura (0, 50, 100 e 150 kg ha-1 N). O aumento na doses de N em cobertura promoveram acréscimo no teor de N foliar, na estimativa do teor de clorofila, no número de grãos por espiga, na massa de 1.000 grãos, na produtividade e no teor de proteína nos grãos de milho. A maior produtividade de grãos foi obtida de acordo com as doses crescentes de N em cobertura juntamente com o espaçamento entre as linhas de 0,80 m e 80.000 plantas ha-1.

Nitrogen fertilization of fall panicum cultivars (Panicum dichotomiflorum Michx.): biochemical and agronomical aspects

São escassas as informações sobre cultivares melhoradas e técnicas culturais adequadas à cultura do painço. Este experimento objetivou avaliar o efeito da aplicação de níveis de nitrogênio (N) em cobertura no desenvolvimento e nos atributos bioquímicos de duas cultivares de painço. Para tanto, instalou-se um experimento em Botucatu (SP), em caixas de cimento amianto, mantidas em túnel plástico. O delineamento experimental foi em blocos casualizados, em esquema fatorial 2x6, com dois cultivares de painço (AL Mogi e AL Tibagi) e seis níveis de adubação nitrogenada (0, 40, 80, 120, 160 e 200 mg L-1), aplicada em cobertura, no início do perfilhamento. Os dois cultivares utilizados tiveram comportamento semelhante em relação às variáveis avaliadas, em resposta à aplicação de N em cobertura. A aplicação de doses de N na cultura do painço proporcionou incrementos nos teores relativos de clorofila, aminoácidos totais, nitrogênio total e altura das plantas, e redução dos teores de açúcares na matéria seca, até o intervalo entre 120 e 160 mg de N L-1. O perfilhamento e produção de grãos tiveram aumento linear com a aplicação de N. A adubação nitrogenada não afetou a produção de matéria seca.

Adubação NK no desenvolvimento e na concentração de macronutrientes no florescimento do feijoeiro

O nitrogênio e o potássio são os elementos mais absorvidos e exportados pelo feijoeiro, sendo a adubação mineral entre os produtores bastante variável quanto as doses aplicadas. Este trabalho avalia os efeitos de doses de N (0, 60, 80, 100 e 120 kg ha-1) e K2O (0, 60 e 120 kg ha-1) no desenvolvimento do feijoeiro, por meio do número de unidades estruturais, peso de material fresco e seco, e a concentração de macronutrientes no florescimento. O experimento foi realizado em Botucatu, SP., em túnel plástico, utilizando-se a cultivar 'Pérola'. Duas plantas foram cultivadas em vasos de 15 L, preenchidos com terra de Latossolo Vermelho Distrófico típico, textura média, por 50 dias. As doses de NK foram parceladas em cobertura aos 20 e 40 dias após semeadura. As variáveis estudadas foram influenciadas pela interação entre as doses de N e K. A adubação parcelada com N via solo, independentemente das doses utilizadas ou da fertilização com K, aumenta a produção de matéria seca sem interferir nos teores de N da parte aérea do feijoeiro, assim como os de K, Ca e Mg. A omissão de N em cobertura reduz o teor de clorofila, diminuindo a produção de matéria seca, mas não interferindo no número de flores. Os níveis de K utilizados não diminuíram os teores de Ca e Mg da planta.

Correlação entre leituras de clorofila e níveis de nitrogênio aplicados em feijoeiro

Foram realizados dois ensaios, sendo um em solução nutritiva e outro em solo, utilizando seis níveis de nitrogênio (28, 56, 84, 112, 140 e 168 mg/L de N) a fim de ajustar as leituras diretas, feitas nas folhas de feijoeiro, com um clorofilômetro (Minolta SPAD-501), aos níveis crescentes de nitrogênio e ao seu teor nas folhas. Avaliaram-se os parâmetros: área foliar; massas dos materiais verde e seco; teor de clorofila; produção de grãos e teores de N, Ca, Mg e S. Todos esses dados, mais as leituras do aparelho, foram correlacionados entre si e com os níveis de N aplicados. As correlações positivas entre as leituras e os níveis de N fornecidos (R = 0,86) e entre as leituras e os teores de N nas folhas (R = 0,75) indicam que há perspectivas favoráveis quanto ao uso desse equipamento para detectar deficiências de nitrogênio em feijoeiro.

Efeito do nitrogenio na nutrição do girassol

Nitrogen (N), besides being one of the macro more absorbed by plants, is the that most limits the production of sunflower. The aim of this study was to evaluate the nutrient content in leaves, grains and nutrient export due to nitrogen levels in sunflower cultivation. A randomized experimental block design consisting of five treatments and four replications: T1 - 50 kg N ha(-1) divided by 10, 20 and 20 kg ha(-1), T2 - 70 kg N ha(-1) divided by 10, 30 and 30 kg ha(-1); T3 - 90 kg N ha(-1) divided by 10, 40 and 40 kg ha(-1), T4 - 110 kg N ha(-1) divided by 10, 50 and 50 kg ha(-1), T5 - 130 kg N ha(-1) divided by 10, 60 and 60 kg ha(-1). These applications were made in installments when sowing and 34 and 48 days after sowing. The parameters were evaluated in leaf nutrient content, nutrient content in grains and nutrient export. Under the experimental conditions it was found that the optimum foliar N were purchased at a dosage above 110 kg ha-1 N. With the increasing amount of N supplied in the sunflower crop was exported over this element, but not at the same rate of increase in dosage. The lowest dose of N the lowest rates of export of P, K, Mg, S, B, Cu, Mn and Zn, while increasing the dose of this nutrient decreased the export of Ca.

Alterações nos teores nutricionais foliares de bananeira 'prata-anã' adubada com composto orgânico em cinco ciclos de produção

O presente trabalho objetivou avaliar o estado nutricional da bananeira-'Prata-anã' durante cinco ciclos de cultivo com adubação orgânica, no município de Botucatu-SP. As plantas foram adubadas com composto orgânico produzido a partir de serragem de madeira e esterco bovino, em que os tratamentos foram constituídos de doses desse composto (0; 98,5; 197,0; 290,5 e 394,0 g de K2O/planta). Empregou-se delineamento experimental em blocos casualizados, com cinco tratamentos e cinco repetições. No florescimento das plantas em cada ciclo, foram retiradas amostras foliares de duas plantas por parcela para serem analisados os teores de nitrogênio, fósforo, potássio, cálcio, magnésio, enxofre, boro, cobre, ferro, manganês e zinco. A maior parte dos macronutrientes presentes nas folhas não foi influenciada pelo incremento de doses de composto orgânico. No decorrer dos ciclos avaliados, os teores foliares de nitrogênio, fósforo, potássio, enxofre, boro, ferro e manganês diminuíram, enquanto o cálcio e o magnésio se acumularam nas plantas. Os teores de potássio estavam abaixo dos padrões para a cultura no Estado de São Paulo, em todos os anos avaliados, mesmo assim as plantas não apresentaram sintomas de deficiência ou queda de produção, inferindo-se que a faixa considerada como adequada para a cultivar pode ser inferior aos padrões atualmente adotados.

Enhanced corrosion resistance of AISI H13 steel treated by nitrogen plasma immersion ion implantation

Electrochemical corrosion measurements of AISI H13 steel treated by Pill process in 3.5% (wt) NaCl solution were investigated. So far the corrosion behavior of AISI H 13 steel by Pill has not been studied. The electrochemical results are correlated with the surface morphology, nitrogen content and hardness of the nitride layer. Ion implantation of nitrogen into H 13 steel was carried out by Pill technique. SEM examination revealed a generalized corrosion and porosity over all analyzed sample surfaces. Penetration of nitrogen reaching more than 20 gm was achieved at 450 degrees C and hardness as high as 1340 HV (factor of 2.7 enhancement over standard tempered and annealed H 13) was reached by a high power, 9 h Pill treatment. The corrosion behavior of the samples was studied by potentiodynamic polarization method. The noblest corrosion behavior was observed for the samples treated by PIII at 450 degrees C, during 9 h. Anodic branches of polarization curves of PIII processed samples show a passive region associated with the formation of a protective film. The passive region current density of PIII treated H13 samples (3.5 x 10(-6) A/cm(2)) is about 270 times lower than the one of untreated specimens, which demonstrates the higher corrosion resistance for the Pill treated H 13 samples. (c) 2007 Elsevier B.V. All rights reserved.