Thesis (M.S.)--Villanova University, 2009. / Biology Dept. Includes bibliographical references.

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Compostos de fósforo insolúveis em água, como os do tipo Fe - K - P podem ser formados em fertilizantes fosfatados totalmente acidulados (FFTA). Em superfosfatos dois dos mais comuns são os compostos Fe3KH8(PO4)6.6H2O (H8) e Fe3KH14(PO4)8.4H2O (H14). Elevadas quantidades de rocha fosfática são descartadas a fim de garantir que FFTA apresentem na fração citrato neutro de amônio (CNA) + água, 90% de P2O5 solúvel em CNA, como prevê a legislação brasileira de fertilizantes. Experimentos anteriores mostraram que os FFTA não necessitam, obrigatoriamente, conter alta solubilidade em água. Estudos anteriores indicaram que rochas fosfáticas poderão ser melhores utilizadas conhecendo-se a performance agronômica das impurezas insolúveis em água. Para adicionar informações a este assunto, os compostos H8 e H14 foram sintetizados em condições de laboratório. Os precipitados foram analisados através de análise química elementar, difratometria de raios-x, microscopia eletrônica de varredura e espectrometria de energia dispersiva (EED). As análises efetuadas confirmaram a correta precipitação de ambos compostos. Um experimento de hidrólise foi conduzido usando soluções de NaCl 0,01; 0,05 e 0,1 mol L -1 com pH variando de 3,0 a 7,5. Amostras do H8, H14 e de FR de Catalão foram agitadas utilizando-se as soluções até pH de equilíbrio. O pH da solução foi ajustado adicionando-se NaOH ou HCl. Depois de atingido o pH de equilíbrio, as soluções foram filtradas, e as concentrações de P, Fe, K, S, Na e Cl determinadas analiticamente e utilizado o programa MINTEQ para calcular a atividade dos íons ortofosfato (H2PO4 - e HPO4 2- ). Os precipitados que ficaram retidos no papel de filtro foram analisados analiticamente e submetidos a raios-x e EED. As quantidades de H8 e H14 sintetizadas foram suficientes para o estudo de hidrólise. Os resultados indicaram que a porcentagem de P liberada dos compostos do tipo Fe - K - P aumentava com o aumento do pH. Quantidades mais elevadas de P foram liberadas do composto H14 quando comparado ao H8. Também, a atividade dos íons ortofosfato foi mais elevada para o H14 quando comparado ao H8. Observou-se uma tendência a elevação da atividade dos íons ortofosfato com a diminuição da força iônica para ambos compostos. Para o H8 ocorreu um aumento da atividade com o aumento do pH para NaCl 0,01 mol L -1 . Para o H14 a tendência foi o aumento da atividade até pH 5,0 para NaCl 0,05 e 0,1 mol L -1 e pH 6,0 para NaCl 0,01 mol L -1 . Após estes valores a atividade tendeu a diminuir devido provavelmente à formação do par NaHPO4 - . As análises químicas, raios-x e EED dos precipitados oriundos do estudo de hidrólise mostraram que os resultados de composição e raios-x são similares ao do composto H8, atestando novamente baixa porcentagem de liberação de P deste composto. Para o composto H14 verificou-se a formação de um novo composto, possivelmente estrengita amorfa. Os dados obtidos neste estudo indicam que elevadas quantidades de P liberado de compostos do tipo Fe - K - P a solução não significam necessariamente elevada atividade. Os resultados confirmam que o composto H14 pode apresentar melhor eficiência agronômica do que o H8. / Water-insoluble P compounds, as of the type Fe-K-P, can be formed in totally acidulated phosphate fertilizers (TAPF). In superphosphates two of the most common are the Fe3KH8(PO4)6.6H2O (H8) and the Fe3KH14(PO4)8.4H2O (H14). High amounts of phosphate rock (PR) are discarded in order to produce APF with about 90% of P2O5 neutral ammonium citrate (NAC) soluble fraction in the available P fraction (NAC + H2O), as indicated by the brazilian fertilizer legislation. Previous experimental data have shown that TAPF do not necessarily need to always contain high water solubility. Studies have indicated that PR will be better utilized by accessing the agronomic performance of water-insoluble P impurities. To add information related to this topic H8 and H14 compounds were synthesized at laboratory conditions. The precipitates were exposed to elemental chemical analysis, x-ray, scanning electron microscope and energy-dispersive spectroscopy (EDS). All chemical plus instrumental analysis confirmed the correct precipitation of both compounds. A hydrolysis experiment was conducted using 0,01; 0,05 and 0,1 mol L -1 NaCl solution with pH ranging from 3 to 7.5. Sub samples of the H8, the H14 and a PR from Catalão were agitated with each solution until certain equilibrium was achieved. Solution pH was adjusted by adding NaOH or HCl. After equilibrium the solutions were filtered, the concentrations of P, Fe, K, S, Na and Cl determined and the software MINTEQ used to calculate the activity of the orthophosphate ions (H2PO4 - and HPO4 2- ). The precipitate remaining in the filter paper was also analyzed for the same elements and submitted to x-ray and EDS. The amounts of H8 and H14 synthesized were enough for the hydrolysis study. The results indicated that the amount of P released from both Fe-K-P compounds increased in higher solution pH. More P was released from the H14 than the H8 compound. Also, the activity for the orthophosphate ions was higher for the H14 than for the H8 compound. There was a trend to obtain higher activity of the ions orthophosphate with lower ionic strength for both compounds. For the H8 it was obtained higher activity as the solution pH increased when the ionic strength was of 0,01 mol L -1 NaCl. For the H14 the trend was for the activity to increase until pH 5 for the 0,05 and 0,1 mol L -1 NaCl solution and until pH 6 for the 0,01 mol L -1 . After these values the activity tended to decrease most likely due to the formation of the NaHPO4 - ionic par. The elemental chemical composition, x-ray and EDS of the precipitates after the hydrolysis study showed composition and x-ray results similar to the H8 compound attesting low hydrolysis in this situation. For the H14 compound it was found the formation of a new compound, most likely an amorphous strengite. Data obtained in this study indicate that higher amounts of P released from compounds of the type Fe-K-P as the solution pH increases does not necessarily mean higher activity. The results confirm that the H14 compound should be of higher agronomic effectiveness than the H8.

Compostos de fósforo insolúveis em água, como os do tipo Fe – K – P podem ser formados em fertilizantes fosfatados totalmente acidulados (FFTA). Em superfosfatos dois dos mais comuns são os compostos Fe3KH8(PO4)6.6H2O (H8) e Fe3KH14(PO4)8.4H2O (H14). Elevadas quantidades de rocha fosfática são descartadas a fim de garantir que FFTA apresentem na fração citrato neutro de amônio (CNA) + água, 90% de P2O5 solúvel em CNA, como prevê a legislação brasileira de fertilizantes. Experimentos anteriores mostraram que os FFTA não necessitam, obrigatoriamente, conter alta solubilidade em água. Estudos anteriores indicaram que rochas fosfáticas poderão ser melhores utilizadas conhecendo-se a performance agronômica das impurezas insolúveis em água. Para adicionar informações a este assunto, os compostos H8 e H14 foram sintetizados em condições de laboratório. Os precipitados foram analisados através de análise química elementar, difratometria de raios-x, microscopia eletrônica de varredura e espectrometria de energia dispersiva (EED). As análises efetuadas confirmaram a correta precipitação de ambos compostos. Um experimento de hidrólise foi conduzido usando soluções de NaCl 0,01; 0,05 e 0,1 mol L -1 com pH variando de 3,0 a 7,5. Amostras do H8, H14 e de FR de Catalão foram agitadas utilizando-se as soluções até pH de equilíbrio. O pH da solução foi ajustado adicionando-se NaOH ou HCl. Depois de atingido o pH de equilíbrio, as soluções foram filtradas, e as concentrações de P, Fe, K, S, Na e Cl determinadas analiticamente e utilizado o programa MINTEQ para calcular a atividade dos íons ortofosfato (H2PO4 - e HPO4 2- ). Os precipitados que ficaram retidos no papel de filtro foram analisados analiticamente e submetidos a raios-x e EED. As quantidades de H8 e H14 sintetizadas foram suficientes para o estudo de hidrólise. Os resultados indicaram que a porcentagem de P liberada dos compostos do tipo Fe – K – P aumentava com o aumento do pH. Quantidades mais elevadas de P foram liberadas do composto H14 quando comparado ao H8. Também, a atividade dos íons ortofosfato foi mais elevada para o H14 quando comparado ao H8. Observou-se uma tendência a elevação da atividade dos íons ortofosfato com a diminuição da força iônica para ambos compostos. Para o H8 ocorreu um aumento da atividade com o aumento do pH para NaCl 0,01 mol L -1 . Para o H14 a tendência foi o aumento da atividade até pH 5,0 para NaCl 0,05 e 0,1 mol L -1 e pH 6,0 para NaCl 0,01 mol L -1 . Após estes valores a atividade tendeu a diminuir devido provavelmente à formação do par NaHPO4 - . As análises químicas, raios-x e EED dos precipitados oriundos do estudo de hidrólise mostraram que os resultados de composição e raios-x são similares ao do composto H8, atestando novamente baixa porcentagem de liberação de P deste composto. Para o composto H14 verificou-se a formação de um novo composto, possivelmente estrengita amorfa. Os dados obtidos neste estudo indicam que elevadas quantidades de P liberado de compostos do tipo Fe – K – P a solução não significam necessariamente elevada atividade. Os resultados confirmam que o composto H14 pode apresentar melhor eficiência agronômica do que o H8. / Water-insoluble P compounds, as of the type Fe-K-P, can be formed in totally acidulated phosphate fertilizers (TAPF). In superphosphates two of the most common are the Fe3KH8(PO4)6.6H2O (H8) and the Fe3KH14(PO4)8.4H2O (H14). High amounts of phosphate rock (PR) are discarded in order to produce APF with about 90% of P2O5 neutral ammonium citrate (NAC) soluble fraction in the available P fraction (NAC + H2O), as indicated by the brazilian fertilizer legislation. Previous experimental data have shown that TAPF do not necessarily need to always contain high water solubility. Studies have indicated that PR will be better utilized by accessing the agronomic performance of water-insoluble P impurities. To add information related to this topic H8 and H14 compounds were synthesized at laboratory conditions. The precipitates were exposed to elemental chemical analysis, x-ray, scanning electron microscope and energy-dispersive spectroscopy (EDS). All chemical plus instrumental analysis confirmed the correct precipitation of both compounds. A hydrolysis experiment was conducted using 0,01; 0,05 and 0,1 mol L -1 NaCl solution with pH ranging from 3 to 7.5. Sub samples of the H8, the H14 and a PR from Catalão were agitated with each solution until certain equilibrium was achieved. Solution pH was adjusted by adding NaOH or HCl. After equilibrium the solutions were filtered, the concentrations of P, Fe, K, S, Na and Cl determined and the software MINTEQ used to calculate the activity of the orthophosphate ions (H2PO4 - and HPO4 2- ). The precipitate remaining in the filter paper was also analyzed for the same elements and submitted to x-ray and EDS. The amounts of H8 and H14 synthesized were enough for the hydrolysis study. The results indicated that the amount of P released from both Fe-K-P compounds increased in higher solution pH. More P was released from the H14 than the H8 compound. Also, the activity for the orthophosphate ions was higher for the H14 than for the H8 compound. There was a trend to obtain higher activity of the ions orthophosphate with lower ionic strength for both compounds. For the H8 it was obtained higher activity as the solution pH increased when the ionic strength was of 0,01 mol L -1 NaCl. For the H14 the trend was for the activity to increase until pH 5 for the 0,05 and 0,1 mol L -1 NaCl solution and until pH 6 for the 0,01 mol L -1 . After these values the activity tended to decrease most likely due to the formation of the NaHPO4 - ionic par. The elemental chemical composition, x-ray and EDS of the precipitates after the hydrolysis study showed composition and x-ray results similar to the H8 compound attesting low hydrolysis in this situation. For the H14 compound it was found the formation of a new compound, most likely an amorphous strengite. Data obtained in this study indicate that higher amounts of P released from compounds of the type Fe-K-P as the solution pH increases does not necessarily mean higher activity. The results confirm that the H14 compound should be of higher agronomic effectiveness than the H8.

Fertilizer applications of urea and triple superphosphate (TSP) may affect availability of plant nutrients in the soil through alteration of soil pH and sorption-displacement effects. The objectives of this experiment were to evaluate urea and TSP effects on nutrient availability to soybean (Glycine max L.). Field experiments were carried out on three Quebec soils; a Chicot sandy clay loam (Gleyed Melanic Brunisol), an Ormstown silty clay loam (Luvic Gleysol) and a Ste. Rosalie clay (Humic Gleysol). Three levels of TSP (0, 40, 80 kg $ rm P sb2O sb5 ha sp{-1}),$ and three levels of urea (0, 25, 50 kg N ha$ sp{-1})$ were incubated in the field and sampled at 4, 8, 12, and 16 weeks. Added TSP increased extractable P and decreased NO$ sb3$-N. Overall, alterations in nutrients other than N and P with added TSP or urea were not agronomically significant. There was increased concentration of N, P and Mo in soybean in some soils due to TSP application. Added urea increased Mg concentration in soybean. The concentration and uptake of Mo was positively correlated with soil extractable P and Mg. Consequently, application of TSP and urea together improved Mo uptake in the Chicot soil, while in slightly acid soils, Ormstown and Ste. Rosalie, TSP alone increased Mo uptake.

Fertilizer applications of urea and triple superphosphate (TSP) suffer from low efficiency for corn production. Band or broadcast application of urea with acidic-P fertilizers may increase fertilizer efficiency. Urea and acidic-P fertilizer interactions in soil-fertilizer microsites were investigated using two Quebec soils. Adding acidic phosphates such as TSP and monoammonium phosphate (MAP) to urea reduced pH in microsites, urea hydrolysis, NH$ sb3$ volatilization, and increased soil NH$ sb4$- and NO$ sb3$-N contents. Ammonia loss decreased as P$ rm sb2O sb5$: urea-N ratios increased. Adding urea to P fertilizer increased soil pH and P sorption when using CaCl$ sb2$ as the electrolyte. Urea application increased 0.5 M NaHCO$ sb3$ extractable P. Banding urea with TSP caused dissolution of organic matter in soils, and increased P diffusion and P concentration in soil solution sampled with filter paper or in 1 M KCl extraction. Two years of field experiments demonstrated that banding urea with TSP or MAP increased soil extractable P (Mehlich-3), N and P nutrient uptake, plant growth and development of corn. Greater P fertilizer efficiencies and higher yields were achieved by banding urea-acidic P fertilizers.

No description available.

No description available.

Urea and triple superphosphate (TSP) are important N and P fertilizers, respectively, but they suffer from inefficiency because of NH$ sb3$ volatilization and phytotoxicity and P fixation. Combinations of urea and TSP or KCl might improve N and P use efficiency primarily through pH changes. Mixtures of urea, TSP and KCl, either compacted or blended, were studied as to NH$ sb3$ volatilization, denitrification and P transformation in soils, and N and P use efficiency in crops. Soils studied included a Ste. Rosalie clay (Humic Gleysol), an Ormstown silty clay loam (Humic Gleysol), a Chicot sandy clay loam (Grey Browm Luvisol), a St. Bernard loam (Melanic Brunisol) and an Upland loamy sand (Humo Ferric Podzol). Triple superphosphate or KCl reduced urease activity and delayed urea hydrolysis primarily through acidification. Ammonia volatilization decreased when urea was surface-applied with TSP or KCl. The depressive effect of TSP on NH$ sb3$ volatilization was reduced and the KCl effect was increased in the soil with high exchangeable acidity. Phytotoxicity from banded urea, NO$ sb2 sp-$ accumulation and denitrification declined with added TSP. Urea hydrolysis caused a rise in pH and dissolution of organic matter in soils, and as a result, Mehlich (3) and water extractable P increased when urea were banded with TSP. Corn yield and N and P use efficiency were improved with application of mixtures of TSP and urea as compared with urea or TSP alone. Compacted mixtures of urea and TSP or KCl were superior to blended mixtures, possible because of the intimate association of fertilizer dissolution products. Compacted mixtures of urea and TSP or KCl hold promise for improved agricultural productions.