Determination of Deposition Order of Toners, Inkjet Inks, and Blue Ballpoint Pen Combining MeV-Secondary Ion Mass Spectrometry and Particle Induced X-ray Emission

Louise Moore, Katherine; Barac, Marko; Brajković, Marko; Bailey, Melanie Jane; Siketić, Zdravko; Bogdanović Radović, Ivančica (2019) Determination of Deposition Order of Toners, Inkjet Inks, and Blue Ballpoint Pen Combining MeV-Secondary Ion Mass Spectrometry and Particle Induced X-ray Emission. Analytical Chemistry, 91 (20). pp. 12997-13005. ISSN 0003-2700

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Official URL: https://pubs.acs.org/doi/10.1021/acs.analchem.9b03...

Abstract

Determination of the deposition order of different writing tools is very important for the forensic investigation of questioned documents. Here we present a novel application of two ion beam analysis (IBA) techniques: secondary ion mass spectrometry using MeV ions (MeV-SIMS) and particle induced X-ray emission (PIXE) to determine the deposition order of intersecting lines made of ballpoint pen ink, inkjet printer ink, and laser printer toners. MeV-SIMS is an emerging mass spectrometry technique where incident heavy MeV ions are used to desorb secondary molecular ions from the uppermost layers of an organic sample. In contrast, PIXE provides information about sample elemental composition through characteristic X-ray spectra coming from greater depth. In the case of PIXE, the information depth depends on incident ion energy, sample matrix and self-absorption of X- rays on the way out from the sample to the X- ray detector. The measurements were carried out using a heavy ion microprobe at the Ruđer Bošković Institute. Principal component analysis (PCA) was employed for image processing of the data. We will demonstrate that MeV-SIMS alone was successful to determine the deposition order of all intersections not involving inkjet printer ink. The fact that PIXE yields information from deeper layers was crucial to resolve cases where inkjet printer ink was included due to its adherence and penetration properties. This is the first time the different information depths of PIXE and MeV-SIMS have been exploited for a practical application. The use of both techniques, MeV- SIMS and PIXE, allowed the correct determination of deposition order for four out of six pairs of samples.

Item Type:

Article

Additional Information:

K.L.M. acknowledges that the project was cofunded by the Erasmus+ program of the European Union. The European Commission's support for the production of this publication does not constitute an endorsement of the contents, which reflects the views only of the authors, and the Commission cannot be held responsible for any use which may be made of the information contained therein. I.B.R. and Z.S. acknowledge support by the HORIZON 2020 Project RADIATE under the Grant Agreement 824096, COST Action Grant CA16101 (Multi -Foresee), and IAEA CRP F11021. The authors also acknowledge Ms. Andrijana Filko from the Forensic Science Center "Ivan VusCetiC" for providing some of the samples and fruitful discussion. M. BrajkoviC acknowledges support by the Croatian Science Foundation Project "Young Researchers' Career Development Project Training of Doctoral Students" cofinanced by the European Union, Operational Program "Efficient Human Resources 2014-2020", and the ESF. M. J. Bailey acknowledges EPSRC Grant EP/R031118/1: Ion Beam Analysis for the 2020s and beyond: An Integration of Elemental Mapping and 'omics', for contributing her time to work on this project

Uncontrolled Keywords:

Deposition Order of Toners ; Inkjet Inks ; Blue Ballpoint Pen ; MeV-SIMS ; PIXE

Subjects:

NATURAL SCIENCES > Physics
NATURAL SCIENCES > Chemistry > Analytic Chemistry

Divisions:

Division of Experimental Physics

Projects:

Project title	Project leader	Project code	Project type
Research And Development with Ion Beams – Advancing Technology in Europe-RADIATE	UNSPECIFIED	824096	EK
UNSPECIFIED	UNSPECIFIED	CRP F11021	IAEA
UNSPECIFIED	UNSPECIFIED	CA16101	COST