A microdestructive capillary electrophoresis method for the analysis of blue-pen-ink strokes on office paper

This manuscript describes the development of a capillary electrophoresis (CE) method for the detection of acid and basic dyes and its application to real samples, blue-pen-ink strokes on office paper. First, a capillary zone electrophoresis (CZE) method was developed for the separation of basic and acid dyes, by studying the separation medium (buffer nature, pH and relative amount of additive) and instrumental parameters (temperature, voltage and capillary dimensions). The method performance was evaluated in terms of selectivity, resolution (above 5 and 2 for acid dyes and basic dyes, respectively, except for two basic dye standards), LOD (lower than 0.4 mg/L) and precision as intraday and interday RSD values of peak migration times (lower than 0.6%). The developed method was then applied to 34 blue pens from different technologies (rollerball, ballpoint, markers) and with different ink composition (gel, water-based, oil-based). A microdestructive sample treatment using a scalpel to scratch 0.3 mg of ink stroke was performed. The entire electropherogram profile allowed the visual discrimination between different types of ink and brands, being not necessary a statistical treatment. A 100% of discrimination was achieved between pen technologies, brands, and models, although non-reproducible zones in the electropherograms were found for blue gel pen samples. The two different batches of blue oil-based pens were also differentiated. Thus, this method provides a simple, microdestructive, and rapid analysis of different blue pen technologies which may complement the current analysis of questioned documents performed by forensic laboratories.