Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry

Abstract

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg⁻¹ (square regression) and 250.0 and 2000.0 μg kg⁻¹ (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg⁻¹, respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.

Keywords:

• Control determination of mercury
• fish and shrimp
• solid sampling
• direct mercury analyzer
• method validation

Acknowledgments

The invaluable contribution of Angelo de Queiroz Mauricio, Maria de Fátima Martins Pinhel and Carolina Costa Mota Paraiba is acknowledged.

Funding

The authors are thankful to the Brazilian Ministry of Agriculture, Livestock and Food Supply for financial support and to Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Brazil) for a scholarship (D.P. Torres).