Cold finger with semi closed reflux system for sample preparation aiming at Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Ni, V and Zn determination in Drinking Water Treatment Sludge by MIP OES.

This study presents method development and optimization, based on statistical approaches, of an alternative sample preparation methodology for Drinking Water Treatment Sludge, through decomposition in semi closed system with cold finger, aiming at the determination of Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Ni, V and Zn by microwave induced plasma optical emission spectrometry. This system was employed to decompose three different Drinking Water Treatment Sludge samples, from three different treatment plants. The compromise conditions were 250 mg of dried sample, 5 mL of HNO3, 1 mL of H2SO4 and heating at 225 °C for 150 min. After the digestion, 1% of cesium and lanthanum chloride buffer solution was added to all samples and standard solutions. The accuracy of the proposed sample preparation method was evaluated by analyzing a sediment certified reference material (CRM NIST 1646a) as well as the spike recovery technique. The recoveries ranged from 83% to 119% for all elements, and the found concentrations for the CRM agreed with the respective certified values, at 95% confidence level. The correlation coefficients for all investigated elements were higher than 0.999. The method LOQ values were adequate and complied with the Drinking Water Treatment Sludge regulation avaliable, ranging from 0.3 (V) and 32 (Zn) µg L-1, or 0.1 (V) to 13 (Zn) mg kg-1. The digestion procedure in acidic medium showed suitable to measure the analytes in the investigated matrix by microwave induced plasma optical emission spectrometry.

Estimate of the uncertainty in measurement for the determination of mercury in seafood by TDA AAS.

An approach for the estimate of the uncertainty in measurement considering the individual sources related to the different steps of the method under evaluation as well as the uncertainties estimated from the validation data for the determination of mercury in seafood by using thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) is proposed. The considered method has been fully optimized and validated in an official laboratory of the Ministry of Agriculture, Livestock and Food Supply of Brazil, in order to comply with national and international food regulations and quality assurance. The referred method has been accredited under the ISO/IEC 17025 norm since 2010. The approach of the present work in order to reach the aim of estimating of the uncertainty in measurement was based on six sources of uncertainty for mercury determination in seafood by TDA AAS, following the validation process, which were: Linear least square regression, Repeatability, Intermediate precision, Correction factor of the analytical curve, Sample mass, and Standard reference solution. Those that most influenced the uncertainty in measurement were sample weight, repeatability, intermediate precision and calibration curve. The obtained result for the estimate of uncertainty in measurement in the present work reached a value of 13.39%, which complies with the European Regulation EC 836/2011. This figure represents a very realistic estimate of the routine conditions, since it fairly encompasses the dispersion obtained from the value attributed to the sample and the value measured by the laboratory analysts. From this outcome, it is possible to infer that the validation data (based on calibration curve, recovery and precision), together with the variation on sample mass, can offer a proper estimate of uncertainty in measurement.

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

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.