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Top-down evaluation of matrix effects uncertainty.

Carla Palma1, Vanessa Morgado2, Ricardo J N Bettencourt da Silva3

  • 1Instituto Hidrográfico, R. Trinas 49, 1249-093 Lisboa, Portugal.

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Summary

This study introduces a method to quantify matrix effects in chemical analysis, revealing they contribute 7.7% to 79% of overall measurement uncertainty. This helps assess if reducing matrix effects improves accuracy and reduces uncertainty.

Keywords:
Matrix effectsMetalsRecoverySedimentsUncertainty

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Area of Science:

  • Analytical Chemistry
  • Environmental Chemistry
  • Metrology

Background:

  • Matrix effects significantly impact chemical measurement accuracy, causing deviations between different sample types.
  • Identifying and quantifying matrix effects is crucial for reducing measurement uncertainty and improving analytical method robustness.

Purpose of the Study:

  • To develop and validate a methodology for estimating the percentage contribution of matrix effects to overall measurement uncertainty.
  • To assess the impact of matrix effects on the uncertainty of trace element analysis in marine sediments.

Main Methods:

  • A novel methodology was developed to estimate matrix effects by comparing intermediate precision with analyte recovery dispersion across different matrices.
  • The measurement model was divided into two intervals (below and above 2x limit of quantification) to account for constant absolute and relative uncertainties.
  • The methodology was applied to analyze Cr, Cu, Li, Mn, Ni, and Pb in marine sediments using established OSPAR and EPA3051A procedures.

Main Results:

  • Matrix effects were found to contribute between 7.7% and 79% to the global measurement uncertainty.
  • In the higher concentration interval (Interval II), relative expanded uncertainties ranged from 12% to 25%, suitable for environmental sediment monitoring.
  • The developed measurement uncertainty models demonstrated compatibility with certified reference materials and proficiency test samples.

Conclusions:

  • The developed methodology provides a reliable way to estimate the contribution of matrix effects to measurement uncertainty.
  • Quantifying matrix effects aids in optimizing analytical procedures, potentially reducing the need for time-consuming methods like standard addition.
  • The findings support the robust environmental monitoring of sediments and offer a transferable tool for other chemical analyses.