POPs Extracted from Shrimp Using Vortex-Assisted MSPD Technique

Scientists from Universidade Federal do Rio Grande in Rio Grande, Brazil created a vortex-assisted matrix solid-phase dispersion (VA-MSPD) method for extracting harmful compounds from shrimp. Their findings were published in the Journal of Chromatography A (1).

Shrimps isolated on white background concept | Image Credit: © petzshadow - stock.adobe.com

Polycyclic aromatic hydrocarbons (PAHs) are a type of persistent organic pollutants (POPs) that are characterized by having at least two condensed aromatic rings in their planar structure. Generated from incomplete combustion or pyrolysis of organic matter, they can arise from natural or anthropogenic sources, including forest fires, industrial processes, or the infiltration of petroleum and coal deposits. These compounds can migrate over long distances and can potentially have carcinogenic or mutagenic effects. This has led to the United States Environmental Protection Agency (USEPA) listing 16 PAHs as POPs: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene, and benzo[ghi]perylene.

PAHs can also accumulate in edible tissues of aquatic organisms, such as shrimp, which is extensively produced in the southern region of Brazil’s Rio Grande do Sul state; further, shrimp is the most consumed seafood globally. In this study, the scientists hoped to optimize and validate an analytical method for extracting priority PAHs from shrimp samples, specifically using vortex-assisted matrix solid-phase dispersion (VA-MSPD) with determination by gas chromatography-tandem mass spectrometry (GC-MS/MS). VA-MSPD improves upon standard MSPD by replacing the packing step by vortex agitation of the sample and solid support mixture with a few mL of the extraction solvent. This reduces inconveniences that stem from the original method, such as the packing of the mixture, and comes with its own advantages, such as reducing the number of necessary steps, less time consumption, and more effective contact between the sample and the solvent.

The optimized method used a reused solid support and was also validated according to National Institute of Metrology, Standardization, and Industrial Quality (INMETRO) and Directorate-General for Health and Food Safety (SANTE) guidelines (2,3), which correspond to the standards bodies for Brazil and the European Union, respectively. The PAHs demonstrated adequate linearity, having correlation coefficients greater than 0.99. The matrix effect was also assessed, with 12 out of the 16 PAHs showing a matrix effect of less than ±20%. The method also had a quantification limit range of 6.67–33.35ng g-1.Accuracy and precision showed recovery values ranging from 55–115% with relative standard deviation (RSD) lower than 17% for all PAHs. When applied, 11 PAHs were detected, including benzo[a]pyrene and benzo[b]fluoranthene, with ∑PAHs ranging from 25.14–79.52 ng g-1. This confirms environmental contamination in the region, hence reinforcing the need for monitoring these contaminants in shrimp destined for human consumption.

Overall, this method was properly optimized and validated, showing the advantages of low cost, to be performed in few steps, use of a reused material, consume low solvent volumes and sample mass. When the VA-MSPD technique was demonstrated for the first time, its suitability, which stemmed from its simplicity and efficiency, showed it to be a notable technique. As such, the scientists now hope it can be applied further to monitoring studies, risk assessment, and PAH occurrence in shrimp and other fishery products.

References

(1) Arias, J. L. de O.; Meireles, A. C. N.; Kulzer, J.; de Oliveira, L. T.; et al. A Vortex-Assisted MSPD Method for the Extraction of Polycyclic Aromatic Hydrocarbons from Shrimp with Determination by GC-MS/MS. J. Chromatogr. A 2024, 1734, 465307. DOI: 10.1016/j.chroma.2024.465307

(2) Inmetro Certification for Brazil. TUV SOD 2024. https://www.tuvsud.com/en-us/services/product-certification/inmetro (accessed 2024-10-4)

(3) Directorate-General for Health and Food Safety (SANTE). EU Monitor 2024. https://www.eumonitor.eu/9353000/1/j9vvik7m1c3gyxp/vjqyn3j6fizb (accessed 2024-10-4)