Now-a-days, various types of antibiotics are being used worldwide in veterinary sector indiscriminately for promotion of growth and treatment of the livestock. Significant portions of antibiotics are released through milk of dairy animals unaltered and exert serious harmful effects on human health. This review evaluates and compare researches on antibiotic residues in milk in published literatures from Pubmed, CrossRef, CAB direct, DOAJ, JournalTOCs, AGRICOLA, ScientificGate, Electronic Journals Library, CAB abstracts, Global Health Databases, Global Impact Factor, Google Scholar, Park Directory of Open Access Journals, BanglaJOL and ISC E-Journals. Antibiotics residue in milk was first detected in 60s and then with an increasing trend with highest after 2,000 (188). The highest no. of works, 49 (21.87%) were accomplished in China, followed by Spain, 30 (13.39%); Germany, 11 (4.91%); and USA, 10 (4.46%). Continent-wise highest researches are published from Europe, 105 (46.88%), followed by Asia, 77 (34.38%); South America, 18 (8.04%); North America, 16 (7.14%); and Africa, 8 (3.57%). For detection, Bovine milk sample is mostly used, 193 (86.16%), followed by ovine, 19 (8.48%); and caprine, 14 (6.25%). Acetonitrile was used in maximum cases (77) for processing the samples. Chromatographic technique was the highest, 115 (51.34%) for detection. Residue of β-lactam group have been detected mostly 133 (36.54%), followed by tetracyclines, 51 (14.01%); fluoroquinolones, 49 (13.46%); sulfonamides, 46 (12.64%); and aminoglycosides, 38 (10.44%). This review observe that antibiotics residues are more common in milk samples that are being manifested in increasing researches on antibiotic detection and measures should adopt to cease this residue.

Antibiotic residues in milk: Past, present, and future.

https://digital.csic.es/bitstream/10261/218705/1/1-s2.0-S0039914014007267-main.pdf

Analytical quality assurance in veterinary drug residue analysis methods: matrix effects determination and monitoring for sulfonamides analysis.

High-throughput method for macrolides and lincosamides antibiotics residues analysis in milk and muscle using a simple liquid-liquid extraction technique and liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-MS/MS).

Sulphonate functionalized covalent organic framework-based magnetic sorbent for effective solid phase extraction and determination of fluoroquinolones.

Determination of sulfonamide antibiotics and metabolites in liver, muscle and kidney samples by pressurized liquid extraction or ultrasound-assisted extraction followed by liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry (HPLC-QqLIT-MS/MS).

A simple, fast and cheap non-SPE screening method for antibacterial residue analysis in milk and liver using liquid chromatography–tandem mass spectrometry

Validation is a required process for analytical methods. However, scope extension, i.e. inclusion of more analytes, other matrices and/or minor changes in extraction procedures, can be achieved without a full validation protocol, which requires time and is laborious to the laboratory. This paper presents a simple and rugged protocol for validation in the case of extension of scope. Based on a previously reported method for analysis of sulfonamide residues using LC-MS/MS, inclusion of more analytes, metabolites, matrices and optimisation for the extraction procedure are presented in detail. Initially, the method was applied only to liver samples. In this work, milk, eggs and feed were also added to the scope. Several case-specific validation protocols are proposed for extension of scope.

Scope extension validation protocol: inclusion of analytes and matrices in an LC-MS/MS sulfonamide residues method

Sulfaquinoxaline (SQX) is a sulfonamide that is widely used in veterinary medicine, with a maximum residue limit (MRL) established for several food matrices. In Brazil, the MRL for liver and muscle is 100 μg kg−1 for equine, bovine, poultry and swine. This value includes not only free drug but also the sum of all metabolites. Several reports showed limitations for SQX residue analysis, especially when mass spectrometry methods were used. These limitations include poor recoveries and unacceptable accuracy responses. In this work a metabolite of SQX, present in liver and kidney samples, was identified. The structure proposed was a hydroxylated form of SQX, called SQX-OH, with an m/z of 317. SQX-OH is also produced in vitro in equine, swine and bovine liver samples. The influence of time, temperature, solvent and dehydration was evaluated in the formation of SQX-OH. Different degrees of hydroxylation were observed in matrices. The N4-acetyl derivates for both SQX and SQX-OH were also detected. In equines, the metabolism of SQX is complete. The mass spectrometry analysis of SQX-OH was determined in vitro using equine liver microsomal fraction. The characterization of this compound was performed using liquid chromatography coupled to mass spectrometry in tandem mode. The fragmentation profile of SQX-OH was seen to be similar to that of the sulfonamides group, producing two high abundant daughter ions: 317 > 156 and 317 > 108, common to most sulfonamides. The main conclusion of this work is that the residue analysis of SQX needs to consider the presence of the SQX-OH in order to give more realistic results, especially when using MRM transitions.

Jéssica Melo

Papers

A simple, fast and cheap non-SPE screening method for antibacterial residue analysis in milk and liver using liquid chromatography–tandem mass spectrometry

Scope extension validation protocol: inclusion of analytes and matrices in an LC-MS/MS sulfonamide residues method

Characterization and estimation of sulfaquinoxaline metabolites in animal tissues using liquid chromatography coupled to tandem mass spectrometry