Handheld SERS coupled with QuEChERs for the sensitive analysis of multiple pesticides in basmati rice

Pesticides are a safety issue globally and cause serious concerns for the environment, wildlife and human health. The handheld detection of four pesticide residues widely used in Basmati rice production using surface-enhanced Raman spectroscopy (SERS) is reported. Different SERS substrates were synthesised and their plasmonic and Raman scattering properties evaluated. Using this approach, detection limits for pesticide residues were achieved within the range of 5 ppb-75 ppb, in solvent. Various extraction techniques were assessed to recover pesticide residues from spiked Basmati rice. Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERs) acetate extraction was applied and characteristic spectral data for each pesticide was obtained from the spiked matrix and analysed using handheld-SERS. This approach allowed detection limits within the matrix conditions to be markedly improved, due to the rapid aggregation of nanogold caused by the extraction medium. Thus, detection limits for three out of four pesticides were detectable below the Maximum Residue Limits (MRLs) of 10 ppb in Basmati rice. Furthermore, the multiplexing performance of handheld-SERS was assessed in solvent and matrix conditions. This study highlights the great potential of handheld-SERS for the rapid on-site detection of pesticide residues in rice and other commodities.

A Wake-Up Call: Determination of Antibiotics Residue Level in Raw Meat in Abattoir and Selected Slaughterhouses in Five Local Government in Kano State, Nigeria.

The frequent use of antibiotics may result in drug residues that can be discovered at varying quantities in animal products such as milk or meat. The presence of pharmaceutical residues in food above the MRLs has been perceived globally by various persons. Antibiotics residues are present in food, which can endanger human health by causing antibiotic sensitivity, allergic reactions, microflora imbalance, bacterial resistance to antibiotics in microorganisms, and financial loss to the food industry. Farmers around the world utilize them on a sporadic basis for both preventative and curative purposes. This study assessed the antibiotics residues in raw meat sold in 6 slaughter houses in Kano States. The study is a descriptive cross-sectional study involving six (6) major slaughter house in Kano state. Muscle, Kidney and liver samples were collected from each slaughterhouse. The antibiotic residues in the meat samples were analysed using high performance liquid chromatography (HPLC) for tetracycline, ciprofloxacin and oxytetracycline residue results were presented in charts and tables. Out of a total of 18 beef samples analyzed during this study, 15 (83%) of the total samples had detectable levels of tetracycline residues from which 6(33.3%) had tetracycline residues at violative levels above the WHO/FAO maximum residue limits (MRLs), out of those 18 beef samples analyzed during this study, 6(33%) of the total samples had detectable levels of oxytetracycline residues from which 3(17%) had oxytetracycline residues at violative levels above the WHO/FAO maximum residue limits (MRLs) and out of those 18 beef samples analyzed during this study, 12(67%) of the total samples had detectable levels of ciprofloxacin, all levels are below the WHO/FAO maximum residue limits (MRLs). This high level of tetracycline and oxytetracycline residues in greater proportion of meat destined for human consumption at violative levels could be as a result of the indiscriminate use and misuse of veterinary drugs as commonly practiced among livestock producers and marketers without observing withdrawal period prior to slaughter. These results indicate that consumers may be predisposed to health hazards and hinder international meat trade from Nigeria. Regulatory authorities should therefore ensure compliance with good agricultural practices including withdrawal period of drugs used for treatment of food animals.

Simultaneous Determination of Amphenicols and Metabolites in Animal-Derived Foods Using Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry

Amphenicols are widely used to prevent and treat animal diseases. However, amphenicol residues accumulate in livestock and poultry and harm consumers. We hypothesized that one can combine solid-phase extraction (SPE) with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to simultaneously determine amphenicols and metabolites in pork, beef, lamb, chicken, and their products and meet government regulations for maximum residue limits. We extracted crude samples with ethyl acetate and ammonia water (98:2, v/v), purified the samples with a CNW Si SPE column, defatted the samples with acetonitrile-saturated n-hexane, and then determined the resulting analytes by UHPLC-MS/MS. The limit of detection of the analytes in livestock and poultry meat was 0.03–1.50 μg/kg, and the limit of quantification was 0.05–5.00 μg/kg. Measured chloramphenicol, thiamphenicol, and florfenicol concentrations were linear over the range 0.50–50 μg/kg; and the florfenicol amine concentration was linear over the range 5.00–200 μg/kg (all with correlation coefficients >0.9990). The recovery of the spiked samples was between 72% and 120%. The intraday relative standard deviation (RSD) ranged from 1% to 9%, and the interday RSD ranged from 1% to 12%. Based on the above results, the current method is sensitive, accurate, and reproducible with the detection limits being well below the maximum residue limits as per Chinese standard GB 31650-2019, and thus, our research hypothesis could be confirmed.

Development of a New Screen-Printed Transducer for the Electrochemical Detection of Thiram

A new transducer based on a screen-printed carbon electrode has been developed for the quantification of thiram. Detection of this fungicide is based on the performance of two enzymes: (1) aldehyde dehydrogenase catalyzes the aldehyde oxidation using NAD+ as a cofactor and simultaneously, (2) diaphorase reoxidizes the NADH formed in the first enzymatic process due to the presence of hexacyanoferrate(III) which is reduced to hexacyanoferrate(II). Taking into account that aldehyde dehydrogenase is inhibited by thiram, the current decreases with pesticide concentration and thiram can be electrochemically quantified below legal limits. The transducer proposed in this work involves the modification of the carbon WE with the co-factors (NAD+ and hexacyanoferrate(III)) required in the enzymatic system. The new device employed in this work allows the detection of 0.09 ppm thiram, a concentration below legal limits (Maximum Residue Limits 0.1–10 ppm).

Determination of patulin in apple juice by liquid chromatography-electrospray tandem mass spectrometry

Patulin is a mycotoxin produced by several fungi, (Penicillium, Aspergillus, Byssochlamys). The main sources of patulin intake in human diet are apples, apple juice and apple nectar, and for this reason, apple based foods are monitored for the presence of this mycotoxin. Commission Regulation EC No 1881/2006 lays down maximum residue limits (MRLs) of 50 µg/kg in apple juice and cider, 25 µg/kg in solid apple products, and 10 µg/kg in products for infants and young children. In Serbia, maximum permitted amounts of patulin in fruit juices, reconstituted concentrated fruit juices and fruit nectars, as well as in solid apple products, including apple compote and apple puree, intended for direct human consumption are prescribed in the Regulation on maximum concentrations of certain contaminants in foodstuffs. This paper presents the LC-MS/MS method for quantitative determination of patulin in apple juice. Criteria for method validation were taken from Commission Decision 2002/657/EC. Linearity was confirmed in the concentration ranges of 0-100 µg/kg, with the limit of detection (LoD) of 9.85 µg/kg. The performance of the method was successfully verified by participating in a proficiency study.

Determination of Eleven Veterinary Drugs in Chicken Meat and Liver

Brazil chicken production is around 13 million tons and about a third is exported to over 150 countries, placing Brazil as the world largest chicken meat producer, and therefore it is crucial to follow the legislation of all importer markets. This study conducted a survey by chance in 45 meat industries able to export. Therefore, 2580 chicken meat samples were collected and submitted to 11 analyte extraction and chromatographic verification of compliance in an accredited laboratory. Ten chemical residues (amoxicillin, bacitracin, colistin, dinitolmide + zoalene, spectinomycin, roxarsone, tiamulin, tylosin, trenbolone acetate and virginiamycin) were investigated in chicken meat and one (halofuginone hydrobromide) in chicken liver. The results showed that no compound exceeded the maximum residue limits established by seven legislations. All residue concentrations found were below the method quantification limit, thereby confirming the capability of Brazilian chicken meat industries in complying to foreign markets.