Rapid and sensitive detection of pharmaceutical pollutants in aquaculture by aluminum foil substrate based SERS method combined with deep learning algorithm

Abstract

Background

Pharmaceutical residual such as antibiotics and disinfectants in aquaculture wastewater have significant potential risks for environment and human health. Surface enhanced Raman spectroscopy (SERS) has been widely used for the detection of pharmaceuticals due to its high sensitivity, low cost, and rapidity. However, it is remain a challenge for high-sensitivity SERS detection and accurate identification of complex pollutants.

Results

Hence, in this work, we developed an aluminum foil (AlF) based SERS detection substrate and established a multilayer perceptron (MLP) deep learning model for the rapid identification of antibiotic components in a mixture. The detection method demonstrated exceptional performance, achieving a high SERS enhancement factor of 4.2 × 10⁵ and excellent sensitivity for trace amounts of fleroxacin (2.7 × 10^-8 mol/L), levofloxacin (1.95 × 10^-8 mol/L), and pefloxacin (6.9 × 10^-8 mol/L),sulfadiazine, methylene blue, and malachite green at a concentration of 1 × 10^-8 mol/L can all be detected, the concentrations of the six target compounds and their Raman intensities exhibit a good linear relationship. Moreover, the AlF SERS substrate can be prepared rapidly without adding organic reagents, and it exhibited good reproducibility, with RSD<9.6%. Additionally, the algorithm model can accurately identify the contaminants mixture of sulfadiazine, methylene blue, and malachite green with a recognition accuracy of 97.8%, an F1-score of 98.2%, and a 5-fold cross validation score of 97.4%, the interpretation analysis using Shapley Additive Explanations (SHAP) reveals that MLP model can specifically concentrate on the distribution of characteristic peaks.

Significance

The experimental results indicated that the MLP model demonstrated strong performance and good robustness in complex matrices. This research provides a promising detection and identification method for the antibiotics and disinfectants in actual aquaculture wastewater treatment.