Ultra-Trace Monitoring of Methylene Blue Degradation via AgNW-Based SERS: Toward Sustainable Advanced Oxidation Water Treatment

Autor(es)

Horta, Isabela ; Neto, Nilton Francelosi Azevedo ; Kito, Leticia Terumi ; Miranda, Felipe ; Thim, Gilmar ; Pereira, Andre Luis de Jesus ; Pessoa, Rodrigo

• Tipo de documento: Artigo Científico
• Fonte: SUSTAINABILITY; v. 17, n. 10, p. 23-pg., 2025-05-14.

Resumo

Methylene blue (MB), a widely used industrial dye, is a persistent pollutant with documented toxicity to aquatic organisms and potential health risks to humans, even at ultra-trace levels. Conventional monitoring techniques such as UV-Vis spectroscopy and fluorescence emission suffer from limited sensitivity, typically failing to detect MB below similar to 10(-7) M. In this study, we introduce a surface-enhanced Raman spectroscopy (SERS) platform based on silver nanowire (AgNW) substrates that enables MB detection over an unprecedented dynamic range-from 1.5 x 10(-4) M down to 1.5 x 10(-16) M. Raman mapping confirmed the presence of individual signal hot spots at the lowest concentration, consistent with the theoretical number of analyte molecules in the probed area, thereby demonstrating near-single-molecule detection capability. The calculated enhancement factors reached up to 1.90 x 10(12), among the highest reported for SERS-based detection platforms. A semi-quantitative calibration curve was established spanning twelve orders of magnitude, and this platform was successfully applied to monitor MB degradation during two advanced oxidation processes (AOPs): TiO2 nanotube-mediated photocatalysis under UV irradiation and atmospheric-pressure dielectric barrier discharge (DBD) plasma treatment. While UV-Vis and fluorescence techniques rapidly lost sensitivity during the degradation process, the SERS platform continued to detect the characteristic MB Raman peak at similar to 1626 cm(-1) throughout the entire treatment duration. These persistent SERS signals revealed the presence of residual MB or partially degraded aromatic intermediates that remained undetectable by conventional optical methods. The results underscore the ability of AgNW-based SERS to provide ultra-sensitive, molecular-level insights into pollutant transformation pathways, enabling time-resolved tracking of degradation kinetics and validating treatment efficiency. This work highlights the importance of integrating SERS with AOPs as a powerful complementary strategy for advanced environmental monitoring and water purification technologies. By delivering an ultra-sensitive, low-cost sensor (<USD 0.16 per test) and promoting reagent-free treatment methods, this study directly advances SDG 6 (Clean Water and Sanitation) and SDG 12 (Responsible Consumption and Production). (AU)

• Processo FAPESP: 22/02994-2 - Projeto Hidrogênio Verde (ProHVer): centro de estudos de fotoeletrodos visando a geração sustentável de H2 combustível
• Beneficiário: André Luis de Jesus Pereira
• Modalidade de apoio: Auxílio à Pesquisa - Projeto Inicial
• Processo FAPESP: 24/15258-8 - Treinamento técnico na técnica SNOM acoplada com AFM/TERS visando o imageamento multimodal da ação do plasma ou da água ativada à plasma na parede celular e de estruturas de microrganismos ou células animais
• Beneficiário: Isabela Machado Horta
• Modalidade de apoio: Bolsas no Brasil - Programa Capacitação - Treinamento Técnico
• Processo FAPESP: 19/05856-7 - Aplicações de plasmas atmosféricos não-térmicos na odontologia: da bancada para a clínica
• Beneficiário: Cristiane Yumi Koga Ito
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 23/02268-2 - Geração e caracterização de diferentes líquidos ativados com plasma para aplicação no tratamento endodôntico
• Beneficiário: Nilton Francelosi Azevedo Neto
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 22/11544-0 - EMU tecnológico: aquisição de um sistema de microscopia óptica de varredura de campo próximo acoplado com microscopia de força atômica e espectroscopia Raman aprimorada por ponta para imageamento químico e físico em micro e nanoescala
• Beneficiário: Rodrigo Savio Pessoa
• Modalidade de apoio: Auxílio à Pesquisa - Programa Infraestrutura - Tecnologia e Inovação