Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers
Autor(a) principal: | |
---|---|
Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/17106 |
Resumo: | Global food security is one of the biggest challenges we face today, and to this end, establishing sustainable strategies towards the development of more efficient and safer agricultural products is indispensable. Sulfur (S) plays an important agronomic role for crops as a secondary macronutrient, and its deficiency in agricultural soils has become an increasing problem for crop productivity and quality. Elemental sulfur (S8) is an abundant byproduct of petroleum refining that stands out as a S-fertilizer. However, S8 can only be assimilated by plants after oxidation by soil microorganisms to sulfate, a slow process that restricts its agronomic efficiency, especially when applied as pellets. Aiming to optimize this conversion, we recently investigated the transformation of the stable S8 structure into a new material with linear S chains using the polymerization technique of inverse vulcanization. The polysulfides (PolyS) showed superior oxidation rates to S8, in addition to interesting processing and conformation characteristics, ideal for the incorporation of other fertilizers. Thus, the primary goal of this work was to evaluate the potential of PolyS as a versatile material with high efficiency as a multifunctional sulfur fertilizer. PolyS pellets were prepared with added porosity to the structure, aiming to increase the surface area for biological oxidation. A study was conducted to understand the interaction of this system with the bacterium Acidithiobacillus thiooxidans, which obtains energy from S oxidation. Moreover, compared to commercial S8 pellets, oxidation in soil was significantly higher from the combined application of the porous PolyS with bacterium. PolyS was also investigated as a dispersant matrix for the controlled-release of other fertilizers, with the advantage of serving as a rich source of S for plants. Composites containing sustainable phosphorus (P) sources with different solubility profiles - phosphate rock and struvite - were synthesized to study the physical and chemical effects of PolyS as a matrix. A synergistic effect between PolyS oxidation and phosphate release was verified, with the local acidity of sulfate generation favoring phosphorus solubilization. The application of PolyS-struvite composites for soybean cultivation was then tested in a greenhouse, with a systematic study of fertilizer effects on root profile and plant development. Compared to conventional soluble sources, PolyS led to higher sulfur uptake efficiency, and the controlled release of P stimulated the production of fine soybean roots. Based on the results it could be concluded that the polysulfides offer versatility for the design of different fertilizer products, with added value as an efficient S source. |
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Valle, Stella Fortuna doOliveira, Caue Ribeiro dehttp://lattes.cnpq.br/5321313558714462http://lattes.cnpq.br/0243366748928079e5970b90-235f-4c1c-aa1f-b0f5416e61e32022-12-02T12:10:40Z2022-12-02T12:10:40Z2022-11-07VALLE, Stella Fortuna do. Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers. 2022. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17106.https://repositorio.ufscar.br/handle/ufscar/17106Global food security is one of the biggest challenges we face today, and to this end, establishing sustainable strategies towards the development of more efficient and safer agricultural products is indispensable. Sulfur (S) plays an important agronomic role for crops as a secondary macronutrient, and its deficiency in agricultural soils has become an increasing problem for crop productivity and quality. Elemental sulfur (S8) is an abundant byproduct of petroleum refining that stands out as a S-fertilizer. However, S8 can only be assimilated by plants after oxidation by soil microorganisms to sulfate, a slow process that restricts its agronomic efficiency, especially when applied as pellets. Aiming to optimize this conversion, we recently investigated the transformation of the stable S8 structure into a new material with linear S chains using the polymerization technique of inverse vulcanization. The polysulfides (PolyS) showed superior oxidation rates to S8, in addition to interesting processing and conformation characteristics, ideal for the incorporation of other fertilizers. Thus, the primary goal of this work was to evaluate the potential of PolyS as a versatile material with high efficiency as a multifunctional sulfur fertilizer. PolyS pellets were prepared with added porosity to the structure, aiming to increase the surface area for biological oxidation. A study was conducted to understand the interaction of this system with the bacterium Acidithiobacillus thiooxidans, which obtains energy from S oxidation. Moreover, compared to commercial S8 pellets, oxidation in soil was significantly higher from the combined application of the porous PolyS with bacterium. PolyS was also investigated as a dispersant matrix for the controlled-release of other fertilizers, with the advantage of serving as a rich source of S for plants. Composites containing sustainable phosphorus (P) sources with different solubility profiles - phosphate rock and struvite - were synthesized to study the physical and chemical effects of PolyS as a matrix. A synergistic effect between PolyS oxidation and phosphate release was verified, with the local acidity of sulfate generation favoring phosphorus solubilization. The application of PolyS-struvite composites for soybean cultivation was then tested in a greenhouse, with a systematic study of fertilizer effects on root profile and plant development. Compared to conventional soluble sources, PolyS led to higher sulfur uptake efficiency, and the controlled release of P stimulated the production of fine soybean roots. Based on the results it could be concluded that the polysulfides offer versatility for the design of different fertilizer products, with added value as an efficient S source.A segurança alimentar mundial é um dos maiores desafios atuais, sendo indispensável para tal estabelecer estratégias sustentáveis que tornem os insumos agrícolas mais eficazes e seguros. O enxofre (S) desempenha um importante papel agronômico para as colheitas como macronutriente secundário, e sua deficiência em solos agrícolas tem se tornado um problema crescente para a produtividade e a qualidade das plantações. O enxofre elementar (S8) é um subproduto abundante do refino do petróleo que tem se destacado como fertilizante. Porém, o S8 só pode ser absorvido pelas plantas após oxidação por microrganismos do solo a sulfato, um processo lento que restringe sua eficiência agronômica, especialmente quando aplicado na forma de pellets. Buscando otimizar a oxidação, investigamos recentemente a transformação da estrutura estável do S8 em um novo material com cadeias lineares de S, usando a técnica de polimerização por vulcanização inversa. Os polissulfetos (PolyS) desenvolvidos demonstraram taxas de oxidação superiores ao S8, além de exibirem características de processamento e conformação interessantes, ideais para veiculação de outros fertilizantes. Assim, este trabalho teve como objetivo principal avaliar o potencial do PolyS como material versátil e com maior eficiência como fertilizante multifuncional de enxofre. Pellets de PolyS com adição de porosidade à estrutura foram preparados visando aumentar a área superficial para a oxidação biológica. Foi estudada a interação desse sistema com a bactéria Acidithiobacillus thiooxidans, que obtém energia a partir da oxidação de S, além da aplicação combinada dos pellets com bactéria em solo, revelando uma oxidação significativamente maior em comparação a pellets comerciais de S8. O PolyS foi investigado também como matriz dispersora para liberação controlada de outros fertilizantes, com a vantagem de servir como fonte rica em S para as plantas. Compósitos contendo fontes sustentáveis de fósforo (P) com diferentes perfis de solubilidade – rocha fosfática e estruvita – foram sintetizados para estudar os efeitos físicos e químicos do PolyS como matriz. Foi verificado um efeito sinergético entre a oxidação do PolyS e a liberação de fosfato, com a acidez local da geração de sulfato favorecendo a solubilização de fósforo. A aplicação de compósitos de PolyS-estruvita para o cultivo da soja foi então testada em casa de vegetação, com estudo sistemático dos efeitos dos fertilizantes no perfil radicular e desenvolvimento vegetal. Comparado a fontes solúveis convencionais, o PolyS levou a uma maior eficiência na absorção de enxofre, e a liberação controlada de P estimulou a produção de raízes finas da soja. A partir dos resultados pôde-se concluir que os polissulfetos oferecem versatilidade para o design de diferentes produtos fertilizantes, com valor agregado como fonte de S eficiente.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CNPq:169057/2018-6CAPES/PrInt: 88887.465567/2019-00engUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessPolissulfetoVulcanização inversaFertilizanteEnxofreFósforoLiberação controladaPolysulfideInverse vulcanizationFertilizerSulfurPhosphorusControlled-releaseCIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICAInvestigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizersInvestigando o potencial de polissulfetos obtidos via vulcanização inversa como fertilizantes sustentáveisinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis6006004dc97aa1-ec0f-4a55-82e1-2ba9ebf71459reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/17106/4/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD54ORIGINALTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdfTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdfapplication/pdf10301936https://repositorio.ufscar.br/bitstream/ufscar/17106/1/Tese%20de%20Doutorado_Stella%20Fortuna%20do%20Valle_com%20pagina%20assinaturas.pdf31b37e5e9d0b376d810d8813c0a2b67fMD51carta-comprovante_homologacao_assinado.pdfcarta-comprovante_homologacao_assinado.pdfCarta comprovante de homologaçãoapplication/pdf58989https://repositorio.ufscar.br/bitstream/ufscar/17106/3/carta-comprovante_homologacao_assinado.pdf922daf38e39f6a1b1cc1f16f021d174fMD53TEXTTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdf.txtTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdf.txtExtracted texttext/plain206282https://repositorio.ufscar.br/bitstream/ufscar/17106/5/Tese%20de%20Doutorado_Stella%20Fortuna%20do%20Valle_com%20pagina%20assinaturas.pdf.txt81cb90375fde4410be545eb2fdc7bb6fMD55carta-comprovante_homologacao_assinado.pdf.txtcarta-comprovante_homologacao_assinado.pdf.txtExtracted texttext/plain959https://repositorio.ufscar.br/bitstream/ufscar/17106/7/carta-comprovante_homologacao_assinado.pdf.txt784fa2ded1dcc1c5d9c293cfa5a1bb79MD57THUMBNAILTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdf.jpgTese de Doutorado_Stella Fortuna do Valle_com pagina assinaturas.pdf.jpgIM Thumbnailimage/jpeg8598https://repositorio.ufscar.br/bitstream/ufscar/17106/6/Tese%20de%20Doutorado_Stella%20Fortuna%20do%20Valle_com%20pagina%20assinaturas.pdf.jpg9425fc95a542172052b20b13ec21ca14MD56carta-comprovante_homologacao_assinado.pdf.jpgcarta-comprovante_homologacao_assinado.pdf.jpgIM Thumbnailimage/jpeg10174https://repositorio.ufscar.br/bitstream/ufscar/17106/8/carta-comprovante_homologacao_assinado.pdf.jpgee925815b56f99c7f7351380c3d69e90MD58ufscar/171062023-09-18 18:32:32.493oai:repositorio.ufscar.br:ufscar/17106Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:32Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.eng.fl_str_mv |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
dc.title.alternative.por.fl_str_mv |
Investigando o potencial de polissulfetos obtidos via vulcanização inversa como fertilizantes sustentáveis |
title |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
spellingShingle |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers Valle, Stella Fortuna do Polissulfeto Vulcanização inversa Fertilizante Enxofre Fósforo Liberação controlada Polysulfide Inverse vulcanization Fertilizer Sulfur Phosphorus Controlled-release CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
title_short |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
title_full |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
title_fullStr |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
title_full_unstemmed |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
title_sort |
Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers |
author |
Valle, Stella Fortuna do |
author_facet |
Valle, Stella Fortuna do |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/0243366748928079 |
dc.contributor.author.fl_str_mv |
Valle, Stella Fortuna do |
dc.contributor.advisor1.fl_str_mv |
Oliveira, Caue Ribeiro de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/5321313558714462 |
dc.contributor.authorID.fl_str_mv |
e5970b90-235f-4c1c-aa1f-b0f5416e61e3 |
contributor_str_mv |
Oliveira, Caue Ribeiro de |
dc.subject.por.fl_str_mv |
Polissulfeto Vulcanização inversa Fertilizante Enxofre Fósforo Liberação controlada |
topic |
Polissulfeto Vulcanização inversa Fertilizante Enxofre Fósforo Liberação controlada Polysulfide Inverse vulcanization Fertilizer Sulfur Phosphorus Controlled-release CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
dc.subject.eng.fl_str_mv |
Polysulfide Inverse vulcanization Fertilizer Sulfur Phosphorus Controlled-release |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
description |
Global food security is one of the biggest challenges we face today, and to this end, establishing sustainable strategies towards the development of more efficient and safer agricultural products is indispensable. Sulfur (S) plays an important agronomic role for crops as a secondary macronutrient, and its deficiency in agricultural soils has become an increasing problem for crop productivity and quality. Elemental sulfur (S8) is an abundant byproduct of petroleum refining that stands out as a S-fertilizer. However, S8 can only be assimilated by plants after oxidation by soil microorganisms to sulfate, a slow process that restricts its agronomic efficiency, especially when applied as pellets. Aiming to optimize this conversion, we recently investigated the transformation of the stable S8 structure into a new material with linear S chains using the polymerization technique of inverse vulcanization. The polysulfides (PolyS) showed superior oxidation rates to S8, in addition to interesting processing and conformation characteristics, ideal for the incorporation of other fertilizers. Thus, the primary goal of this work was to evaluate the potential of PolyS as a versatile material with high efficiency as a multifunctional sulfur fertilizer. PolyS pellets were prepared with added porosity to the structure, aiming to increase the surface area for biological oxidation. A study was conducted to understand the interaction of this system with the bacterium Acidithiobacillus thiooxidans, which obtains energy from S oxidation. Moreover, compared to commercial S8 pellets, oxidation in soil was significantly higher from the combined application of the porous PolyS with bacterium. PolyS was also investigated as a dispersant matrix for the controlled-release of other fertilizers, with the advantage of serving as a rich source of S for plants. Composites containing sustainable phosphorus (P) sources with different solubility profiles - phosphate rock and struvite - were synthesized to study the physical and chemical effects of PolyS as a matrix. A synergistic effect between PolyS oxidation and phosphate release was verified, with the local acidity of sulfate generation favoring phosphorus solubilization. The application of PolyS-struvite composites for soybean cultivation was then tested in a greenhouse, with a systematic study of fertilizer effects on root profile and plant development. Compared to conventional soluble sources, PolyS led to higher sulfur uptake efficiency, and the controlled release of P stimulated the production of fine soybean roots. Based on the results it could be concluded that the polysulfides offer versatility for the design of different fertilizer products, with added value as an efficient S source. |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-12-02T12:10:40Z |
dc.date.available.fl_str_mv |
2022-12-02T12:10:40Z |
dc.date.issued.fl_str_mv |
2022-11-07 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
VALLE, Stella Fortuna do. Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers. 2022. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17106. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/17106 |
identifier_str_mv |
VALLE, Stella Fortuna do. Investigating the potential of polysulfides obtained via inverse vulcanization as sustainable fertilizers. 2022. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17106. |
url |
https://repositorio.ufscar.br/handle/ufscar/17106 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
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600 600 |
dc.relation.authority.fl_str_mv |
4dc97aa1-ec0f-4a55-82e1-2ba9ebf71459 |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química - PPGQ |
dc.publisher.initials.fl_str_mv |
UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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