A mathematical formulation for a gravimetric approach to the univariate standard addition method (SAM) is presented that has general applicability for both liquids and solids. Using gravimetry rather than volumetry reduces the preparation time, increases design flexibility, and makes increased accuracy possible. SAM has most often been used with analytes in aqueous solutions that are aspirated into flames or plasmas and determined by absorption, emission, or mass spectrometric techniques. The formulation presented here shows that the method can also be applied to complex matrixes, such as distillate and residual fuel oils, using techniques such as X-ray fluorescence (XRF) or combustion combined with atomic fluorescence or absorption. These techniques, which can be subject to matrix-induced interferences, could realize the same benefits that have been demonstrated for dilute aqueous solutions.
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