Novel modified QuEChERS combined with UPLC-MS/MS technology for the detection of antibiotic residues in several common kinds of aquaculture products

Aquatic products play an important role in human diet. Compared with other livestock and poultry products, aquatic products are featured with low fat content, high protein content, and easy digestion. Therefore, aquatic products are deeply loved by consumers. Generally speaking, aquatic products can be divided into two categories: naturally caught aquatic products and aquaculture aquatic products. In recent years, with the decline of marine resources and the increase of marine pollution, aquaculture is booming. In order to improve the efficiency of aquaculture, antibiotics are usually used, which brings risk to human health. Therefore, the monitoring of antibiotic residues in aquaculture products has been an important part in the field of food safety. To supervise antibiotic residues in aquaculture products, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) combined with UPLC-MS/MS for the simultaneous determination of 28 antibiotic residues in aquaculture products was established, with nano grapheme oxide/multi walled carbon nanotubes (n-GO/MWCNTs) composite as the adsorbent. Moreover, parameters such as the ratio of acetonitrile and methanol in extractant, the amount of the n-GO/MWCNTs, were optimized through the recovery of 28 antibiotics. Besides, the adsorbent action of n-GO/MWCNTs was also compared with PSA, C18, MWCNTs, and graphene. Finally, method validation was accomplished according to Codex guideline (CAC/GL-71) with the following performance characteristics: the linearity, limit of detection and quantification, matrix effects, recovery, intra-day and inter-day precision. The results showed that the absorption effect of n-GO/MWCNTs was the best with acetonitrile: methanol (75∶25, V/V) and 10 mg of n-GO/MWCNTs. Good linearity (R²>0.99) was observed for all tested antibiotics with the limit of detection and quantification were 0.06-1.42 μg/kg and 0.20-4.72 μg/kg. Low matrix effects (<10%) was observed for most tested drugs (except for SIA, SQX, DAN and LOM). The average recovery of this protocol was 80.1%-100.4% in the spiked levels of 5-100 μg/kg. The intra-day precision was lower than 10.3%, while the inter-day precision below 13.4%. Method applications authenticated that the established method had favorable repeatability and high sensitivity, which could be applied to the regulatory routine analysis. We hope this work could provide technical support for the monitoring of antibiotic residues in aquaculture products and be helpful to the quality and safety control of aquaculture products.