Multi-element quantification of ancient/historic glasses by laser ablation inductively coupled plasma mass spectrometry using sum normalization calibration

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for quantitative analysis of ancient/historic glasses is subject to calibration issues which have been addressed in this work. Since ancient/historic glasses have widely ranging matrix compositions, a complementary analysis by an alternative method is generally employed to determine at least one major element which can be used as an internal standard. We demonstrate that such a complementary analysis is unnecessary using a so-called sum normalization calibration technique (mathematically formulated) by simultaneous measurement of 54 elements and normalizing them to 100% [w/w] based on their corresponding oxide concentrations. The crux of this approach is that by assuming a random internal standard concentration of a particular major oxide, e.g. SiO2, the normalization algorithm varies the internal standard concentration until the cumulated concentrations of all 54 elemental oxides reach 100% [w/w]. The fact that 54 elements are measured simultaneously predetermines the laser ablation mode to rastering. Nine glass standards, some replicating historic compositions, were used for calibration. The linearity of the calibration graphs (forced through the origin) represented by the relative standard deviations in the slope were between 0.1 and 6.6% using SiO2 as an internal standard. This allows high-accuracy determination of elemental oxides as confirmed by good agreement between found and reported values for major and minor elemental oxides in some synthetic glasses with typical medieval composition (European Science Foundation 151 and 158). Also for trace elemental concentrations of lanthanides in a reference glass (P&H Developments Ltd. DLH7, a base glass composition with nominally 75 μg g−1 elements added) accurate data were obtained.Interferences from polyatomic species and doubly charged species on the masses of trace elements are possible, depending on the base composition of the glass, with Ba and Sb glasses showing potential interferences on some lanthanides. We showed that they may be reduced to a great extent by using an Octopole Reaction System although the overall sensitivity decreases which may be a problem for some low-level determinations.