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

Author(s)

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

• Document type: Journal article
• Source: SUSTAINABILITY; v. 17, n. 10, p. 23-pg., 2025-05-14.

Abstract

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)

• FAPESP's process: 22/02994-2 - Green hydrogen project (ProHVer): photoelectrode study center aiming the sustainable generation of H2 fuel
• Grantee: André Luis de Jesus Pereira
• Support Opportunities: Research Grants - Initial Project
• FAPESP's process: 24/15258-8 - Technical training in the SNOM technique coupled with AFM/TERS aiming at multimodal imaging of the action of plasma or plasma-activated water on the cell wall and structures of microorganisms or animal cells
• Grantee: Isabela Machado Horta
• Support Opportunities: Scholarships in Brazil - Technical Training Program - Technical Training
• FAPESP's process: 19/05856-7 - Use of low temperature atmospheric pressure plasma in dentistry: from laboratory bench to clinics
• Grantee: Cristiane Yumi Koga Ito
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 23/02268-2 - Generation and characterization of different liquids activated with plasma for use in endodontic treatment
• Grantee: Nilton Francelosi Azevedo Neto
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 22/11544-0 - Technological EMU: acquisition of a near-field scanning optical microscopy system coupled with atomic force microscopy and tip-enhanced Raman spectroscopy for chemical and physical imaging at micro and nanoscale
• Grantee: Rodrigo Savio Pessoa
• Support Opportunities: Research Infrastructure Program - Technology and Innovation