O trabalho teve por objetivo avaliar o aproveitamento e a distribuição do nitrogênio e do enxofre adicionado ao solo como fertilizante no sistema solo-cana-de-açúcar (cana-planta), utilizando-se os isótopos estáveis 15N e 34S . Objetivou-se também avaliar a contribuição do nitrogênio mineralizado dos resíduos culturais marcados em 15N e incorporados ao solo, numa condição próxima a de reforma de canavial sem despalha a fogo. Foram quantificadas as perdas por lixiviação de N e S proveniente do solo e dos fertilizantes, com verificação da resposta em produção e qualidade da cana-planta à adubação com N e S no plantio, e realizado o balanço final do N e S no sistema solo-cana-de-açúcar. A pesquisa foi desenvolvida na Estação Experimental Apta 15 em Piracicaba/SP, com o uso de vasos plásticos de 220 L preenchidos com aproximadamente 250 kg de solo de textura arenosa. Foram realizados, simultaneamente, dois experimentos em delineamento experimental de blocos casualizados com quatro repetições. O primeiro experimento constituiu-se de um fatorial completo 4 X 2 (quatro doses de N: 0, 1,2, 2,4 e 3,6 g N vaso-1 e duas doses de S: 0 e 2,1 g S vaso-1 ) e com aplicação de fertilizantes marcados isotopicamente (15N - 10% em átomos e 34S- 9,5% em átomos) e resíduos culturais (folhas secas, ponteiros e raízes + rizomas) sem marcação isotópica. O segundo experimento constituiu-se de cinco tratamentos com a combinação dos níveis de N e S, com a diferença de terem recebido resíduo cultural com marcação isotópica (15N- 0,827% em átomos). Na camada superficial de terra (0-25cm) foram adicionados os restos culturais e o calcário. Após a calagem foi realizada a aplicação dos tratamentos e o plantio com o transplante de três gemas por vaso da cultivar de cana-de-açúcar SP 80-3280. Os experimentos tiveram duração de 16 meses. O aumento na extração de N, proporcionado pelo aumento das doses de N-fertilizante resultou em sinergismo na extração de S. Nas condições do trabalho, com limitação da nutrição nitrogenada da canaplanta, a fertilização com S associada à de N não resultou em efeito sinérgico na produtividade da cultura; entretanto houve resposta em produtividade às doses crescentes de N, sem haver resposta à aplicação de S. A lixiviação de S (S-fertilizante e S-nativo do solo) diminuiu com o aumento das doses de N. O balanço final para o N indicou aproveitamento pelas plantas de 35% do Nfertilizante e 14% dos resíduos culturais, com efeito residual do N dessas fontes de 34 e 75% do N respectivamente. O N não contabilizado no sistema foi de 10 e 31% , respectivamente, para as fontes N-resíduo cultural e N-fertilizante, o que se atribuiu a possíveis perdas de amônia por volatilização do solo e pela parte aérea e, também, a desnitrificação. Para o balanço final de S verificou-se aproveitamento de 32% do S-fertilizante pelas plantas, com efeito residual no solo de 43% da fertilização. O S não contabilizado no sistema atingiu valor máximo de 10% do total aplicado, sendo atribuído à perda por volatilização de SO2 pela parte aérea da cana-de-açúcar. / This work\'s objective was to evaluate the use and distribution of nitrogen and sulfur added to the soil as fertilizers in the soil-sugarcane system (plant cane), using the stable isotopes 15N and 34S. The study also aimed to evaluate the contribution of nitrogen mineralized from sugar cane crop residues labeled with 15N and incorporated into the soil, in a condition similar to that found in the renovation of a sugarcane plantation without burning the trash. Losses of N and S from the soil and from the fertilizers via leaching were quantified. Sugarcane responses in terms of yield and plant cane quality to N and S fertilization at planting were determined, and the N and S final balances in the soil-sugarcane system were calculated. The research was conducted at the Apta 15 Experiment Station in Piracicaba/SP, using 220 L-capacity plastic pots filled with approximately 250 kg of a sandy-textured soil. Two experiments were conducted simultaneously in a random block experimental design with four replicates. The first experiment consisted of a full 4 X 2 factorial arrangement (four N doses: 0, 1.2, 2.4, and 3.6 g N pot-1 and two S doses: 0 and 2.1 g S pot-1) and application of isotopically labeled fertilizers (15N- 10% in atoms and 34S-9.5% in atoms) and crop residues (dry leaves, shoots and roots + rhizomes) without isotopic labeling. The second experiment consisted of five treatments involving those N and S level combinations, except that they received isotopically labeled crop residues (15N- 0.827% in atoms). Crop residues and lime were added to the soil surface layer (0-25cm). The treatments were applied after liming, and planting was accomplished by transplanting three buds per pot of sugarcane cultivar SP 80-3280. The experiments lasted 16 months. The increased N extraction provided by increased fertilizer N doses resulted in S-extraction synergism. In the conditions of this study, under nitrogen nutrition limitation in plant cane, S fertilization in association with N fertilization did not result in a synergistic crop productivity effect; however, there was a productivity response to increasing N doses, without response to S application. S leaching (fertilizer S and native S from the soil) decreased as N doses increased. The final N balance indicated a 35% utilization by plants of fertilizer-N and 14% of crop residue-N, with residual effects in those sources of 34 and 75% N, respectively. The unaccounted N in the system were 10 and 31%, respectively, for crop residue-N and fertilizer-N sources, which were attributed to ammonia losses by volatilization from the soil and via the above-ground part of the plant, and to denitrification. A 32% utilization of fertilizer-S by the plants was verified in the final S balance, with a residual effect in the soil of 43% of fertilization. S not accounted for in the system reached a maximum value of 10% of the total applied, attributed to losses by SO2 volatilization via the above-ground part of the sugarcane plants.

O trabalho teve por objetivo avaliar o aproveitamento e a distribuição do nitrogênio e do enxofre adicionado ao solo como fertilizante no sistema solo-cana-de-açúcar (cana-planta), utilizando-se os isótopos estáveis 15N e 34S . Objetivou-se também avaliar a contribuição do nitrogênio mineralizado dos resíduos culturais marcados em 15N e incorporados ao solo, numa condição próxima a de reforma de canavial sem despalha a fogo. Foram quantificadas as perdas por lixiviação de N e S proveniente do solo e dos fertilizantes, com verificação da resposta em produção e qualidade da cana-planta à adubação com N e S no plantio, e realizado o balanço final do N e S no sistema solo-cana-de-açúcar. A pesquisa foi desenvolvida na Estação Experimental Apta 15 em Piracicaba/SP, com o uso de vasos plásticos de 220 L preenchidos com aproximadamente 250 kg de solo de textura arenosa. Foram realizados, simultaneamente, dois experimentos em delineamento experimental de blocos casualizados com quatro repetições. O primeiro experimento constituiu-se de um fatorial completo 4 X 2 (quatro doses de N: 0, 1,2, 2,4 e 3,6 g N vaso-1 e duas doses de S: 0 e 2,1 g S vaso-1 ) e com aplicação de fertilizantes marcados isotopicamente (15N - 10% em átomos e 34S- 9,5% em átomos) e resíduos culturais (folhas secas, ponteiros e raízes + rizomas) sem marcação isotópica. O segundo experimento constituiu-se de cinco tratamentos com a combinação dos níveis de N e S, com a diferença de terem recebido resíduo cultural com marcação isotópica (15N- 0,827% em átomos). Na camada superficial de terra (0-25cm) foram adicionados os restos culturais e o calcário. Após a calagem foi realizada a aplicação dos tratamentos e o plantio com o transplante de três gemas por vaso da cultivar de cana-de-açúcar SP 80-3280. Os experimentos tiveram duração de 16 meses. O aumento na extração de N, proporcionado pelo aumento das doses de N-fertilizante resultou em sinergismo na extração de S. Nas condições do trabalho, com limitação da nutrição nitrogenada da canaplanta, a fertilização com S associada à de N não resultou em efeito sinérgico na produtividade da cultura; entretanto houve resposta em produtividade às doses crescentes de N, sem haver resposta à aplicação de S. A lixiviação de S (S-fertilizante e S-nativo do solo) diminuiu com o aumento das doses de N. O balanço final para o N indicou aproveitamento pelas plantas de 35% do Nfertilizante e 14% dos resíduos culturais, com efeito residual do N dessas fontes de 34 e 75% do N respectivamente. O N não contabilizado no sistema foi de 10 e 31% , respectivamente, para as fontes N-resíduo cultural e N-fertilizante, o que se atribuiu a possíveis perdas de amônia por volatilização do solo e pela parte aérea e, também, a desnitrificação. Para o balanço final de S verificou-se aproveitamento de 32% do S-fertilizante pelas plantas, com efeito residual no solo de 43% da fertilização. O S não contabilizado no sistema atingiu valor máximo de 10% do total aplicado, sendo atribuído à perda por volatilização de SO2 pela parte aérea da cana-de-açúcar. / This work\'s objective was to evaluate the use and distribution of nitrogen and sulfur added to the soil as fertilizers in the soil-sugarcane system (plant cane), using the stable isotopes 15N and 34S. The study also aimed to evaluate the contribution of nitrogen mineralized from sugar cane crop residues labeled with 15N and incorporated into the soil, in a condition similar to that found in the renovation of a sugarcane plantation without burning the trash. Losses of N and S from the soil and from the fertilizers via leaching were quantified. Sugarcane responses in terms of yield and plant cane quality to N and S fertilization at planting were determined, and the N and S final balances in the soil-sugarcane system were calculated. The research was conducted at the Apta 15 Experiment Station in Piracicaba/SP, using 220 L-capacity plastic pots filled with approximately 250 kg of a sandy-textured soil. Two experiments were conducted simultaneously in a random block experimental design with four replicates. The first experiment consisted of a full 4 X 2 factorial arrangement (four N doses: 0, 1.2, 2.4, and 3.6 g N pot-1 and two S doses: 0 and 2.1 g S pot-1) and application of isotopically labeled fertilizers (15N- 10% in atoms and 34S-9.5% in atoms) and crop residues (dry leaves, shoots and roots + rhizomes) without isotopic labeling. The second experiment consisted of five treatments involving those N and S level combinations, except that they received isotopically labeled crop residues (15N- 0.827% in atoms). Crop residues and lime were added to the soil surface layer (0-25cm). The treatments were applied after liming, and planting was accomplished by transplanting three buds per pot of sugarcane cultivar SP 80-3280. The experiments lasted 16 months. The increased N extraction provided by increased fertilizer N doses resulted in S-extraction synergism. In the conditions of this study, under nitrogen nutrition limitation in plant cane, S fertilization in association with N fertilization did not result in a synergistic crop productivity effect; however, there was a productivity response to increasing N doses, without response to S application. S leaching (fertilizer S and native S from the soil) decreased as N doses increased. The final N balance indicated a 35% utilization by plants of fertilizer-N and 14% of crop residue-N, with residual effects in those sources of 34 and 75% N, respectively. The unaccounted N in the system were 10 and 31%, respectively, for crop residue-N and fertilizer-N sources, which were attributed to ammonia losses by volatilization from the soil and via the above-ground part of the plant, and to denitrification. A 32% utilization of fertilizer-S by the plants was verified in the final S balance, with a residual effect in the soil of 43% of fertilization. S not accounted for in the system reached a maximum value of 10% of the total applied, attributed to losses by SO2 volatilization via the above-ground part of the sugarcane plants.

Arsenic and antimony are important trace elements in magmatic-hydrothermal systems, geothermal systems and epithermal deposits, but their partitioning behavior between melt and aqueous fluid is not well understood. The partitioning of arsenic and antimony between aqueous fluid and granitic melt has been studied in the system SiO2-Al2O3-Na2O-K2O-H2O at 800 degree C and 200 MPa. The partition coefficients of As and Sb between aqueous fluid and melt, are 1.4 +- 0.5 and 0.8 +- 0.5, respectively. The partitioning of As is not affected by aluminum saturation index (ASI) or SiO2 content of the melt, or by oxygen fugacity under oxidized conditions (log fO2 > the nickel-nickel oxide buffer, NNO). The partitioning of Sb is independent of and SiO2 content of the melt. However, aluminum saturation index (ASI) does affect Sb partitioning and Sb partition coefficient for peralkaline melt (0.1 +- 0.01) is much smaller than that for metaluminous melts (0.8 +- 0.4) and that for peraluminous melts (1.3 +- 0.7). Thermodynamic calculations show that As(III) is dominant in aqueous fluid at 800 degree C and 200 MPa and XPS analysis of run product glass indicate that only As(III) exists in melt, which confirms the finding that does not affect As partitioning between fluid and melt. XPS analysis of run product glass show that Sb(V) is dominant in melt at oxidized conditions (log fO2 > -10). The peralkaline effect only exhibits on Sb partitioning, not on As partitioning at oxidized conditions, which is consistent with the x-ray photoelectron spectroscopy (XPS) measurements that As(III) and Sb(V) are dominant oxidation states in melt under oxidized conditions, because the peralkaline effect is stronger for pentavalent than trivalent cations. Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon (OC) column showed an initial sulfate reduction rate of 0.4 μmol g(oc)-1 d-1 and exhausted its capacity to promote sulfate reduction after 30 pore volumes (PVs), or 9 months of flow. The Fe0-bearing organic carbon (FeOC) column sustained a relative constant sulfate reduction rate of 0.9 μmol g(oc)-1 d-1 for at least 65 PVs (17 months). The microbial enumerations and isotopic measurements indicate that the sulfate reduction was mediated by sulfate reducing bacteria (SRB). The cathodic production of H2 by anaerobic corrosion of Fe probably is the cause of the difference in sulfate reduction rates between the two reactive mixtures. Zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs and Fe0-bearing organic carbon reactive mixture has a potential to improve the performance of organic carbon PRBs. The δ34S values can be used to determine the extent of sulfate reduction, but the fractionation is not consistent between reactive materials. The δ13C values indicate that methanogenesis is occurring in the front part of both columns. Arsenic and antimony in groundwater are great threats to human health. The PRB technology potentially is an efficient and cost-effective approach to remediate organic and inorganic contamination in groundwater. Two column experiments were conducted to assess the rates and capacities of organic carbon (OC) PRB and Fe-bearing organic carbon (FeOC) PRB to remove As and Sb under controlled groundwater flow conditions. The average As removal rate for the OC column was 13 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity was 11 μmole g-1 (dry weight of organic carbon). The remove rate of the FeOC material was 165 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity was 105 mole g-1 (dry weight of organic carbon). Antimony removal rate of the OC material decreases from 8.2 to 1.4 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity is 2.4 μmole g-1 (dry weight of organic carbon). The minimum removal rate of FeOC material is 13 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity is 8.4 μmole g-1 (dry weight of organic carbon). The As(III) : [As(III)+As(V)] ratio increased from 1% in the influent to 50% at 5.5 cm from the influent end, and to 80% at 15.5 cm from the influent end of the OC column. X-ray absorption near edge spectroscopy (XANES) shows As(III)-sulfide species on solid samples. These results suggest that As(V) is reduced to As(III) both in pore water and precipitate as As sulfides or coprecipitate with iron sulfides. The arsenic reduction rate suggests that As(V) reduction is mediated by bacterial activity in the OC column and that both abiotic reduction and bacterial reduction could be important in FeOC.

Arsenic and antimony are important trace elements in magmatic-hydrothermal systems, geothermal systems and epithermal deposits, but their partitioning behavior between melt and aqueous fluid is not well understood. The partitioning of arsenic and antimony between aqueous fluid and granitic melt has been studied in the system SiO2-Al2O3-Na2O-K2O-H2O at 800 degree C and 200 MPa. The partition coefficients of As and Sb between aqueous fluid and melt, are 1.4 +- 0.5 and 0.8 +- 0.5, respectively. The partitioning of As is not affected by aluminum saturation index (ASI) or SiO2 content of the melt, or by oxygen fugacity under oxidized conditions (log fO2 > the nickel-nickel oxide buffer, NNO). The partitioning of Sb is independent of and SiO2 content of the melt. However, aluminum saturation index (ASI) does affect Sb partitioning and Sb partition coefficient for peralkaline melt (0.1 +- 0.01) is much smaller than that for metaluminous melts (0.8 +- 0.4) and that for peraluminous melts (1.3 +- 0.7). Thermodynamic calculations show that As(III) is dominant in aqueous fluid at 800 degree C and 200 MPa and XPS analysis of run product glass indicate that only As(III) exists in melt, which confirms the finding that does not affect As partitioning between fluid and melt. XPS analysis of run product glass show that Sb(V) is dominant in melt at oxidized conditions (log fO2 > -10). The peralkaline effect only exhibits on Sb partitioning, not on As partitioning at oxidized conditions, which is consistent with the x-ray photoelectron spectroscopy (XPS) measurements that As(III) and Sb(V) are dominant oxidation states in melt under oxidized conditions, because the peralkaline effect is stronger for pentavalent than trivalent cations. Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon (OC) column showed an initial sulfate reduction rate of 0.4 μmol g(oc)-1 d-1 and exhausted its capacity to promote sulfate reduction after 30 pore volumes (PVs), or 9 months of flow. The Fe0-bearing organic carbon (FeOC) column sustained a relative constant sulfate reduction rate of 0.9 μmol g(oc)-1 d-1 for at least 65 PVs (17 months). The microbial enumerations and isotopic measurements indicate that the sulfate reduction was mediated by sulfate reducing bacteria (SRB). The cathodic production of H2 by anaerobic corrosion of Fe probably is the cause of the difference in sulfate reduction rates between the two reactive mixtures. Zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs and Fe0-bearing organic carbon reactive mixture has a potential to improve the performance of organic carbon PRBs. The δ34S values can be used to determine the extent of sulfate reduction, but the fractionation is not consistent between reactive materials. The δ13C values indicate that methanogenesis is occurring in the front part of both columns. Arsenic and antimony in groundwater are great threats to human health. The PRB technology potentially is an efficient and cost-effective approach to remediate organic and inorganic contamination in groundwater. Two column experiments were conducted to assess the rates and capacities of organic carbon (OC) PRB and Fe-bearing organic carbon (FeOC) PRB to remove As and Sb under controlled groundwater flow conditions. The average As removal rate for the OC column was 13 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity was 11 μmole g-1 (dry weight of organic carbon). The remove rate of the FeOC material was 165 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity was 105 mole g-1 (dry weight of organic carbon). Antimony removal rate of the OC material decreases from 8.2 to 1.4 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity is 2.4 μmole g-1 (dry weight of organic carbon). The minimum removal rate of FeOC material is 13 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity is 8.4 μmole g-1 (dry weight of organic carbon). The As(III) : [As(III)+As(V)] ratio increased from 1% in the influent to 50% at 5.5 cm from the influent end, and to 80% at 15.5 cm from the influent end of the OC column. X-ray absorption near edge spectroscopy (XANES) shows As(III)-sulfide species on solid samples. These results suggest that As(V) is reduced to As(III) both in pore water and precipitate as As sulfides or coprecipitate with iron sulfides. The arsenic reduction rate suggests that As(V) reduction is mediated by bacterial activity in the OC column and that both abiotic reduction and bacterial reduction could be important in FeOC.

Le colza est une oléagineuse très exigeante en soufre (S). L'étude des impacts de limitations en S sur la physiologie du colza et sa qualité grainière revêt un intérêt majeur dans un contexte de baisse des dépôts atmosphériques entrainant un appauvrissement des sols en S. Les objectifs étaient donc d'étudier l'incidence d'une limitation en S sur la physiologie de jeunes feuilles, et sur la qualité, le métabolisme soufré et la vigueur germinative des graines. L'analyse physiologique (photosynthèse, flux de S par utilisation de traceur ³⁴S-sulfate), protéomique et biochimique (métabolites S, espèces réactives de l'O₂) a démontré qu'une limitation en S provoque des perturbations du métabolisme carboné et soufré de la feuille et de la graine, pouvant affecter la qualité grainière. Ainsi, une restriction en S au stade rosette se traduit par la chute de l'activité photosynthétique des jeunes feuilles et conduit à un stress oxydatif. Des restrictions en S à différents stades reproducteurs altèrent la qualité protéique et lipidique de la graine aboutissant à une accumulation amoindrie des acides oléique, linoléique, linolénique et des protéines de stockage (SSPs) riches en S. Une accumulation accrue de SSPs pauvres en S permet un maintien de la teneur en protéines de la graine en cas de restriction survenant en fin de cycle. L'accumulation de S dans les protéines de la graine apparaît principalement contrôlée par la synthèse protéique. La vigueur germinative des graines produites est réduite en cas de restriction précoce en S. Ces travaux ont également permis de démontrer que le péricarpe et la graine en développement sont capables d'assimiler le sulfate par la voie réductrice.