Os solos brasileiros, assim como aqueles localizados em regiões tropicais, possuem elevada capacidade de sorver fósforo (P) devido ao alto grau de intemperismo e consequente composição mineralógica da fração argila. Os fertilizantes solúveis possuem baixa eficiência em função da rápida adsorção aos minerais presentes nestes solos, como também precipitação com cátions em solução. Um componente do solo que pode diminuir a sorção de P é a matéria orgânica que atua na formação de complexos organominerais, inativando os sítios de adsorção dos minerais. Assim, a adição de biocarvão, um composto orgânico recalcitrante, mas que possui grupos reativos de superfície, pode contribuir na redução da sorção de P no solo. O objetivo do trabalho foi estudar o efeito de diferentes temperaturas de pirólise nas características químicas e adsortivas do biocarvão e disponibilidade e aproveitamento de fósforo do fertilizante aplicado no solo. Os biocarvões foram produzidos por pirólise do bagaço de cana-de-açúcar a 250, 450, 650 ºC e um carvão comercial de eucalipto foi utilizado como controle. Os biocarvões foram caracterizados quimicamente e agitados com soluções contendo diferentes doses de P para verificar o comportamento da adsorção de P (isoterma de adsorção). Após filtragem, os biocarvões retidos no filtro foram submetidos à espectroscopia no infravermelho médio. Foram realizados: (i) Um experimento de incubação, fatorial 4 x 2 x 2 + controle, utilizando um solo contendo 70 g kg-1 de argila, com os tratamentos: 4 tipos de biocarvão aplicados na dose de 10 g kg-1; dois níveis de pH (4,8 e 5,8) e dois níveis de adubação fosfatada (0 e 50 mg kg-1). As análises realizadas no solo foram pH em solução de CaCl2 e SMP, P disponível e P remanescente. (ii) Um experimento em casa-de-vegetação, fatorial 4 x 3 x 4, com cultivo de plantas de feijão avaliando os 4 tipos de biocarvão produzidos, 3 doses de cada biocarvão (0, 450 e 900 mg kg-1) aplicados na linha de semeadura e 4 doses de P (0, 25, 50 e 100 mg kg-1) aplicadas contato com o biocarvão na linha. Não houve adsorção de P pelos biocarvões avaliados. Os espectros de infravermelho e análise química mostram que o aumento da temperatura causa diminuição da acidez total, porém aumenta aromaticidade e superfície específica dos materiais. No experimento de incubação os solos que receberam biocarvões produzidos com bagaço de cana apresentaram maior P disponível e remanescente, por mecanismos diferentes. Enquanto o biocarvão produzido à 250 ºC promove a redução da adsorção por interações promovidas por grupos ácidos, os biocarvões com estruturas aromáticas formam complexos de ligações não covalentes com os minerais. O biocarvão pode ser um material importante na redução da sorção de fósforo e economia de fertilizantes, porém pesquisas adicionais devem ser realizadas a fim de estudar a influência da matéria-prima e forma de produção nas potencialidades de uso do produto obtido. / The Brazilian soils, as those from tropical environment, have high phosphorus (P) sorption capacity as a result of their weathering degree and consequently the mineralogical composition in the clay fraction. Soluble fertilizers have low efficiency since the fast adsorption occurs in mineral surfaces, as well as precipitation with cations in the soil solution. The organic matter acts decreasing P sorption in the soils after form organomineral complexes with minerals, by inactivation of adsorption sites. In this way, biochar that is a recalcitrant organic compost; however, contains surface reactive functional groups, can contribute decreasing soil P sorption. The aim of this work was to study the effect of different pyrolysis temperatures in biochar adsorption characteristics, P availability in the soil and plant P absorption from phosphate fertilizer. Biochars were produced by pyrolysis of sugarcane bagasse at 250, 450, 650 ºC and eucalyptus biochar was used as control treatment. Biochars were chemically characterized, and after mixed with solutions containing different P concentrations to study the P sorption behaviour (adsorption isotherm). After filtering, the biochars retained in the filters were undergoing to medium infrared spectroscopy. Were performed: (i) Incubation experiment, factorial 4 x 2 x 2 + control in a soil containing 70 g kg- 1 of clay, with the following treatments: the 4 biochar types cited above, applied at 10 g kg-1 rate; 2 pH levels (4,8 and 5,8) and 2 levels of phosphate fertilizer (0 and 50 mg kg-1). The soil pH (CaCl2 salt and SMP), available and remaining P were analysed. (ii) Greenhouse experiment was performed in 4 x 3 x 4 factorial scheme, with cultivation of common bean plants to evaluate the produced biochars; 3 biochar rates (0, 450 and 900 mg kg-1) were applied at the sowing line and 4 P rates (0, 25, 50 and 100 mg kg-1) added in the same line. The evaluated biochars do not adsorb P. Infrared spectroscopy and chemical analysis showed that increasing temperature resulted in a decreasing in the total acidity. However, occurred an increase in the aromaticity and specific surface of materials. Incubation experiment revealed that the soils which received biochar produced by sugarcane bagasse have greater available and remaining P, these influenced by different mechanisms. While biochar produced at 250 ºC promote adsorption reduction by interactions between biochar acid functional groups and mineral adsorption sites, biochars produced at high temperatures contain aromatic structures can complex minerals by noncovalent bonding. Biochar can be an important tool to reduce P sorption and increase the economy of fertilizers. However, further researches must be carried out to study the influence of feedstocks and pyrolysis technology in the potentiality of use of each biochar.

Os solos brasileiros, assim como aqueles localizados em regiões tropicais, possuem elevada capacidade de sorver fósforo (P) devido ao alto grau de intemperismo e consequente composição mineralógica da fração argila. Os fertilizantes solúveis possuem baixa eficiência em função da rápida adsorção aos minerais presentes nestes solos, como também precipitação com cátions em solução. Um componente do solo que pode diminuir a sorção de P é a matéria orgânica que atua na formação de complexos organominerais, inativando os sítios de adsorção dos minerais. Assim, a adição de biocarvão, um composto orgânico recalcitrante, mas que possui grupos reativos de superfície, pode contribuir na redução da sorção de P no solo. O objetivo do trabalho foi estudar o efeito de diferentes temperaturas de pirólise nas características químicas e adsortivas do biocarvão e disponibilidade e aproveitamento de fósforo do fertilizante aplicado no solo. Os biocarvões foram produzidos por pirólise do bagaço de cana-de-açúcar a 250, 450, 650 ºC e um carvão comercial de eucalipto foi utilizado como controle. Os biocarvões foram caracterizados quimicamente e agitados com soluções contendo diferentes doses de P para verificar o comportamento da adsorção de P (isoterma de adsorção). Após filtragem, os biocarvões retidos no filtro foram submetidos à espectroscopia no infravermelho médio. Foram realizados: (i) Um experimento de incubação, fatorial 4 x 2 x 2 + controle, utilizando um solo contendo 70 g kg-1 de argila, com os tratamentos: 4 tipos de biocarvão aplicados na dose de 10 g kg-1; dois níveis de pH (4,8 e 5,8) e dois níveis de adubação fosfatada (0 e 50 mg kg-1). As análises realizadas no solo foram pH em solução de CaCl2 e SMP, P disponível e P remanescente. (ii) Um experimento em casa-de-vegetação, fatorial 4 x 3 x 4, com cultivo de plantas de feijão avaliando os 4 tipos de biocarvão produzidos, 3 doses de cada biocarvão (0, 450 e 900 mg kg-1) aplicados na linha de semeadura e 4 doses de P (0, 25, 50 e 100 mg kg-1) aplicadas contato com o biocarvão na linha. Não houve adsorção de P pelos biocarvões avaliados. Os espectros de infravermelho e análise química mostram que o aumento da temperatura causa diminuição da acidez total, porém aumenta aromaticidade e superfície específica dos materiais. No experimento de incubação os solos que receberam biocarvões produzidos com bagaço de cana apresentaram maior P disponível e remanescente, por mecanismos diferentes. Enquanto o biocarvão produzido à 250 ºC promove a redução da adsorção por interações promovidas por grupos ácidos, os biocarvões com estruturas aromáticas formam complexos de ligações não covalentes com os minerais. O biocarvão pode ser um material importante na redução da sorção de fósforo e economia de fertilizantes, porém pesquisas adicionais devem ser realizadas a fim de estudar a influência da matéria-prima e forma de produção nas potencialidades de uso do produto obtido. / The Brazilian soils, as those from tropical environment, have high phosphorus (P) sorption capacity as a result of their weathering degree and consequently the mineralogical composition in the clay fraction. Soluble fertilizers have low efficiency since the fast adsorption occurs in mineral surfaces, as well as precipitation with cations in the soil solution. The organic matter acts decreasing P sorption in the soils after form organomineral complexes with minerals, by inactivation of adsorption sites. In this way, biochar that is a recalcitrant organic compost; however, contains surface reactive functional groups, can contribute decreasing soil P sorption. The aim of this work was to study the effect of different pyrolysis temperatures in biochar adsorption characteristics, P availability in the soil and plant P absorption from phosphate fertilizer. Biochars were produced by pyrolysis of sugarcane bagasse at 250, 450, 650 ºC and eucalyptus biochar was used as control treatment. Biochars were chemically characterized, and after mixed with solutions containing different P concentrations to study the P sorption behaviour (adsorption isotherm). After filtering, the biochars retained in the filters were undergoing to medium infrared spectroscopy. Were performed: (i) Incubation experiment, factorial 4 x 2 x 2 + control in a soil containing 70 g kg- 1 of clay, with the following treatments: the 4 biochar types cited above, applied at 10 g kg-1 rate; 2 pH levels (4,8 and 5,8) and 2 levels of phosphate fertilizer (0 and 50 mg kg-1). The soil pH (CaCl2 salt and SMP), available and remaining P were analysed. (ii) Greenhouse experiment was performed in 4 x 3 x 4 factorial scheme, with cultivation of common bean plants to evaluate the produced biochars; 3 biochar rates (0, 450 and 900 mg kg-1) were applied at the sowing line and 4 P rates (0, 25, 50 and 100 mg kg-1) added in the same line. The evaluated biochars do not adsorb P. Infrared spectroscopy and chemical analysis showed that increasing temperature resulted in a decreasing in the total acidity. However, occurred an increase in the aromaticity and specific surface of materials. Incubation experiment revealed that the soils which received biochar produced by sugarcane bagasse have greater available and remaining P, these influenced by different mechanisms. While biochar produced at 250 ºC promote adsorption reduction by interactions between biochar acid functional groups and mineral adsorption sites, biochars produced at high temperatures contain aromatic structures can complex minerals by noncovalent bonding. Biochar can be an important tool to reduce P sorption and increase the economy of fertilizers. However, further researches must be carried out to study the influence of feedstocks and pyrolysis technology in the potentiality of use of each biochar.

Wildland fire, which includes both planned (prescribed fire) and unplanned (wildfire) fires, is an important component of many ecosystems. Prescribed burning (controlled burning) is used as an effective tool in managing a variety of ecosystems in the United States to reduce accumulation of hazardous fuels, manage wildlife habitats, mimic natural fire occurrence, manage traditional native foods, and provide other ecological and societal benefits. During wildland fires, both live and dead (biomass) plants undergo a two-step thermal degradation process (pyrolysis and combustion) when exposed to high temperatures. Pyrolysis is the thermal decomposition of organic material, which does not require the presence of oxygen. Pyrolysis products may later react with oxygen at high temperatures, and form flames in the presence of an ignition source. In order to improve prescribed fire application, accomplish desired fire effects, and limit potential runaway fires, an improved understanding of the fundamental processes related to the pyrolysis and ignition of heterogeneous fuel beds of live and dead plants is needed.In this research, fast pyrolysis of 14 plant species native to the forests of the southern United States has been studied using a flat-flame burner (FFB) apparatus. The results of fast pyrolysis experiments were then compared to the results of slow pyrolysis experiments. The plant species were selected, which represent a range of common plants in the region where the prescribed burning has been performed. The fast pyrolysis experiments were performed on both live and dead (biomass) plants using three heating modes: (1) convection-only, where the FFB apparatus was operated at a high heating rate of 180 °C s-1 (convective heat flux of 100 kW m-2) and a maximum fuel surface temperature of 750 °C; (2) radiation-only, where the plants were pyrolyzed under a moderate heating rate of 4 °C s-1 (radiative heat flux of 50 kW m-2), and (3) a combination of radiation and convection, where the plants were exposed to both convective and radiative heat transfer mechanisms. During the experiments, pyrolysis products were collected and analyzed using a gas chromatograph equipped with a mass spectrometer (GC-MS) for the analysis of tars and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) for the analysis of light gases.The results showed that pyrolysis temperature, heating rate, and fuel type, have significant impacts on the yields and the compositions of pyrolysis products. These experiments were part of a large project to determine heat release rates and model reactions that occur during slow and fast pyrolysis of live and dead vegetation. Understanding the reactions that occur during pyrolysis then can be used to develop more accurate models, improve the prediction of the conditions of prescribed burning, and improve the prediction of fire propagation.

Prescribed (i.e., controlled) burning is a common practice used in many vegetation types in the world to accomplish a wide range of land management objectives including wildfire risk reduction, wildlife habitat improvement, forest regeneration, and land clearing. To properly apply controlled fire and reduce unwanted fire behavior, an improved understanding of fundamental processes related to combustion of live and dead vegetation is needed. Since the combustion process starts with pyrolysis, there is a need for more data and better models of pyrolysis of live and dead fuels. In this study, slow pyrolysis experiments were carried out in a pyrolyzer apparatus and a Thermogravimetric analyzer (TGA) under oxygen free environment in three groups of experiments. In the first group, the effects of temperature (400–800 °C), a slow heating rate (H.R.) (5–30 °C min−1), and carrier gas flow rate (50–350 ml min−1) on yields of tar and light gas obtained from pyrolysis of dead longleaf pine litter in the pyrolyzer apparatus were investigated to find the optimum condition which results in the maximum tar yield. In the second group of experiments, 14 plant species (live and dead) native to forests in the southern United States, were heated in the pyrolyzer apparatus at the optimum condition. A gas chromatograph equipped with a mass spectrometer (GC–MS) and a gas chromatograph equipped with a thermal conductivity detector (GC-TCD) were used to study the speciation of tar and light gases, respectively. In the third group of experiments, the slow pyrolysis experiments for all plant species (live and dead) were carried out in the TGA at 5 different heating rates ranged from 10 to 30 ℃ min-1 to study the kinetics of pyrolysis. The results showed that the highest tar yield was obtained at a temperature of 500 °C, heating rate of 30 °C min−1, and sweep gas flow rate of 100 ml min−1. In addition, the tar composition is dominated by oxygenated aromatic compounds consisting mainly of phenols. The light gas analysis showed that CO and CO2 were the dominant light gas species for all plant samples on a dry wt% basis, followed by CH4 and H2. The kinetics of pyrolysis was studied using one model-free method and three model-fitting methods. First, the model-free method of Kissinger-Akahira-Sunose (KAS) was used to calculate the rates of pyrolysis as a function of the extent of conversion. The results showed that different plant species had different rates at different conversions. Then, three model fitting methods were used to find the kinetic parameters to potentially provide a single rate for each plant species. The results showed that the simple one-step model did not fit the one-peak pyrolysis data as well as the distributed activation energy model (DAEM) model. The multiple-reaction DAEM model provided very good fits to the experimental data where multiple peaks were observed, even at different heating rates.