Ballpoint Pen Inks Study: a review for the Forensic Approach in Questioned Documents

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Roberta Petry Gorziza
Carina Maria Bello de Carvalho
Marina González
Rafael Scorsatto Ortiz
Renata Pereira Limberger

Abstract

Inside Questioned Documents scope, ballpoint pen inks analysis demands analytical methods knowledge, as well as data results interpretation. This review aims to clarify about these techniques, also presenting recent research studies in this area. It can contribute to a better understanding of these approaches and to support forensic reports by Questioned Documents Experts. The knowledge about separation techniques, like chromatography, mass spectrometry techniques, spectroscopy techniques and multivariate statistics are fundamental to solve judicial questions about pen inks analysis.

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How to Cite
Ballpoint Pen Inks Study: a review for the Forensic Approach in Questioned Documents. Brazilian Journal of Police Sciences, Brasília, Brasil, v. 13, n. 9, p. 207–234, 2022. DOI: 10.31412/rbcp.v13i9.867. Disponível em: https://periodicos.pf.gov.br/index.php/RBCP/article/view/867.. Acesso em: 24 nov. 2024.
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Author Biographies

Roberta Petry Gorziza, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS, Brazil / Student | Florida International University, Miami-FL, United States of America / Postdoctoral Researcher

PhD in Pharmaceutical Sciences from the Federal University of Rio Grande do Sul (UFRGS), where she also completed her Master's in Genetics and Molecular Biology and a Bachelor's Degree in Biomedicine. Postgraduate in Criminal Forensics and Forensic Sciences by the Graduate Institute (IPOG). She has expertise in Human Genetics, Hematology, Pathology, Oncology and Clinical Research. She is a Judicial Expert registered at the Court of Justice of Rio Grande do Sul since 2015, working in expertise related to the biomedical area (clinical and toxicological analysis, genetics and molecular biology) and the area of forensic documents. She is currently a postdoctoral researcher at Florida International University, working in the field of Forensic Toxicology.

Carina Maria Bello de Carvalho, Polícia Federal, Porto Alegre-RS, Brazil / Federal Criminal Expert

Possui Doutorado e Mestrado do Programa de Pós Graduação em Ciências Farmacêuticas pela Faculdade de Farmácia Universidade Federal do Rio Grande do Sul (UFRGS).  Graduação na Faculdade de Farmácia da Universidade Federal do Rio Grande do Sul (2001). Tem experiência na área de Farmácia, com ênfase em Ciências Farmacêuticas, atuando principalmente nos seguintes temas: informação sobre medicamentos, bulas, epidemiologia, valepotriatos e valeriana. Possui experiência em Perícia Criminal, atuando principalmente nas áreas de Química Forense e Toxicologia, Genética Forense e Documentoscopia.

Marina González, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS, Brazil / Scholarship

Graduated in Analytical Toxicology from the Federal University of Health Sciences of Porto Alegre - UFCSPA (2014), Specialist in Criminal Expertise and Forensic Sciences from the Graduate Institute - IPOG (2016). Master in Pharmaceutical Sciences from the Federal University of Rio Grande do Sul - UFRGS (2018). She is currently a member of the Brazilian Society of Forensic Sciences, affiliated with the Brazilian Academy of Forensic Sciences and Judicial Expert of the Court of Justice of Rio Grande do Sul. She defended her Doctorate by the Graduate Program in Pharmaceutical Sciences at UFRGS on March 29, 2022. She has experience in the areas of Forensic Science, Analytical Chemistry, Forensic Chemistry, Analytical Toxicology, Forensic Toxicology, Clinical Toxicology and Papilloscopy.

Rafael Scorsatto Ortiz, Polícia Federal, Porto Alegre-RS, Brasil / Federal Criminal Expert

Post-Doctorate in Pharmaceutical Sciences from UFRGS with research on the subject of drug counterfeiting and toxicology of drugs of abuse, developing analytical methodologies that allow detection and traceability, seeking to support the creation of forensic intelligence. Federal Criminal Expert of the Federal Police (since 2004) working in the area of ​​laboratory expertise (drugs, medicines, pesticides, etc.) and crime scene. Graduated in Pharmacy from UFRGS (1998), with emphasis on Medicines Industry (2000). He holds a Masters in Pharmaceutical Sciences from UFRGS (2003) and a Specialization in Forensic Toxicology from Centro Universitário Feevale (2009). His Doctoral Thesis "Chemical and technological profile of counterfeit drugs: a multivariate statistical approach to the cases of Viagra and Cialis?" was ranked first at the 4th National Meeting of Forensic Chemistry (ENQFor) in 2014, receiving the Forensic Highlight Award He is co-author of the book "Toxicologia Forense", which was awarded the Best Book in the area of ​​Forensic Sciences (2014/2015), receiving the Forensic Highlight Award in 2016. He is a member of the Management Committee of INCT Forense, of the Management Unit Strategy and Development Training Team of the Federal Police Superintendence in Rio Grande do Sul. It has more than 70 articles published in the forensic area.

Renata Pereira Limberger, Universidade Federal do Rio Grande do Sul, Porto Alegre-RS, Brazil / Retired Professor

Pharmacist (UFRGS, 1994) with specialization in Toxicology (PUCRS, 2003), Master's (PPGCF/UFRGS, 1996) and Doctorate (PPGCF/UFRGS, 2001) in Pharmaceutical Sciences and Post-Doctorate in Chemistry (IQ/UNICAMP, 2004). Retired Professor at the Federal University of Rio Grande do Sul (Department of Analysis, UFRGS), where she worked as a master's, doctoral and postdoctoral supervisor at the Graduate Program in Pharmaceutical Sciences at the Federal University of Rio Grande do Sul (PPGCF/UFRGS), member of the National Institute of Forensic Science and Technology (INCT-Forense), member of the Academic Network of Health Sciences of Lusophony (Coimbra, Portugal) and Co-editor of Pharmaceutical Sciences of the International Scientific Journal of the Academic Network of Sciences of Lusophony Health (RevSALUS).

How to Cite

Ballpoint Pen Inks Study: a review for the Forensic Approach in Questioned Documents. Brazilian Journal of Police Sciences, Brasília, Brasil, v. 13, n. 9, p. 207–234, 2022. DOI: 10.31412/rbcp.v13i9.867. Disponível em: https://periodicos.pf.gov.br/index.php/RBCP/article/view/867.. Acesso em: 24 nov. 2024.

References

ALMEIDA, Camila M. et al. Study of chemical profile and of lines crossing using blue and black ink pens by LDI (+) MS and LDI (+) imaging. Microchemical Journal, v. 148, p. 220–229, 2019. DOI: 10.1016/j.microc.2019.05.002

AMADOR, Victoria Silva; et al. Paper Spray Mass Spectrometry for the Forensic Analysis of Black Ballpoint Pen Inks. Journal of American Society of Mass Spectrometry, v. 28, 1965Y1976, 2017. DOI: 10.1007/s13361-017-1686-z

BAYGILDIEVA, D.I.; et al. Studying of Handwritten Strokes Aging Kinetics by High-Performance Liquid Chromatography–Mass Spectrometry. Journal of Analytical Chemistry, v. 74(13), p. 1263-1270, 2019. DOI: 10.1134/S1061934819130033

BÖCK, Fernanda Carla. et al. Photometrix and colorimetric image analysis using smartphones. Journal of Chemometrics, v. 34, p. e3251, 2020. DOI: 10.1002/cem.3251

BORBA, Flávia de Souza Lins. et al. Confocal Raman imaging and chemometrics applied to solve forensic document examination involving crossed lines and obliteration cases by a depth profiling study. Analyst, v. 142, p. 1106-1118, 2017. DOI: 10.1039/c6an02340a.

BORBA, Flávia de Souza Lins; HONORATO, Ricardo Saldanha; JUAN, Ana de. Use of Raman spectroscopy and chemometrics to distinguish blue ballpoint pen inks. Forensic Science International, v. 249, p. 73-82, 2015. DOI: 10.1016/j.forsciint.2015.01.027

BRITO, Livia Rodrigues. et al. Evaluating the potential of near infrared hyperspectral imaging associated with multivariate data analysis for examining crossing ink lines. Forensic Science International, v. 298, p. 169–176, 2019. DOI: 10.1016/j.forsciint.2019.02.043

BRITO, Livia Rodrigues. et al. Critical review and trends in forensic investigations of crossing ink lines. TrAC Trends in Analytical Chemistry, v. 94, p. 54-69, 2017. DOI:10.1016/J.TRAC.2017.07.005

BÜGLER, Jürgen H.; BUCHNER, Hans; DALLMAYER, Anton. Age Determination of Ballpoint Pen Ink by Thermal Desorption and Gas Chromatography–Mass Spectrometry. Journal of Forensic Science, v. 53 (4), p. 982-988, 2008. DOI: 10.1111/j.1556-4029.2008.00745.x

CALCERRADA, Matias; GARCIA-RUIZ, Carmen. Analysis of questioned documents: A review. Analytica Chimica Acta, v. 853, n. 1, p. 143–166, 2015. DOI: 10.1016/j.aca.2014.10.057

CÂMARA & SILVA, Erick Simões; FEUERHARMEL, Samuel. Documentoscopia: Aspectos Científicos, Técnicos e Jurídicos. 1ª Edição. São Paulo: Millenium Editora, 2014.

CARVALHO, Carina Maria Bello de. et al. Application of Multivariate Statistics (PCA and HCA) on Ballpoint Pen Inks Infrared Spectra for Dating of Forensic Relevant Documents. Journal of American Society of Questioned Documents Examiners, v. 22(1), p. 19-35, 2019.

CARVALHO, Carina Maria Bello de; ORTIZ, Rafael Scorsatto; LIMBERGER, Renata Pereira. Manuscripts from Different Brands of Ballpoint Pens – GC/MS Ageing Profile in Brazilian Tropical Weather. Current Chromatography, v. 6(1), p.1-20, 2019. DOI: 10.2174/2213240606666190410152956

CARVALHO, Carina Maria Bello de. et al. Characterization and Differentiation of Ballpoint Pen Ink Strokes on Paper Using Orbitrap Mass Spectrometry and Multivariate Statistic. Forensic Science & Addiction Research, v. 2, n. 2, p. 1-8, 2018. DOI: 10.31031/FSAR.2018.02.000537

CARVALHO, Carina Maria Bello de; et al. Using GC/MS to Detect Caffeine in Real Case of Artificially Aged Forged Documents and Method Optimization. Current Chromatography, v. 5, p. 53-64, 2018a. DOI: 10.2174/2213240605666180216145033

CARVALHO, Carina Maria Bello de; ORTIZ, Rafael Scorsatto; LIMBERGER, Renata Pereira. Figures of Merit Evaluation of GC/MS Method for Quantification of 2- Phenoxyethanol from Ballpoint Pen Ink Lines and Determination of the Influence of Support Paper on Solvent Extraction. Química Nova, v. 42, n. 1, p. 42-48, 2018. DOI: 10.21577/0100-4042.20170308

CARVALHO, Carina Maria Bello de. Análise da concentração basal dos solventes de tintas de canetas esferográficas. Revista Brasileira de Ciências Policiais, v. 5, n.1, p.65-96, 2014.

COPPER, Christine. et al. Analysis of ballpoint pen inks directly from paper using capillary Electrophoresis. Forensic Chemistry, v. 13, e100145, 2020. DOI: 10.1016/j.chroma.2015.04.036

COSTA, Karina F.F. et al. Document ink dye age estimation by direct injection-mass spectrometry and correlation analysis. Microchemical Journal, v. 147, p. 1123–1132, 2019. DOI: 10.1016/j.microc.2019.04.034

DEL PICCHIA FILHO, José; DEL PICCHIA, Celso Mauro Ribeiro; DEL PICCHIA, Ana Maura Gonçalves. Tratado de Documentoscopia: da falsidade documental. 3ª Edição. São Paulo: Editora Pillares, 2016.

DEGANI, Ana Luiza; CASS, Quezia; VIEIRA, Paulo. Cromatografia: um breve ensaio. Química Nova na Escola, v. 7, p. 21-25, 1998.

DENMAN, John; et al. Organic and inorganic discrimination of ballpoint pen inks by ToF-SIMS and multivariate statistics. Applied Surface Science, v. 256, p. 2155-2163, 2010. DOI: 10.1016/j.apsusc.2009.09.066

DÍAZ-SANTANA, Oscar; CONDE-HARDISSON, Francisco; VEGA-MORENO, Daura. Comparison of the main dating methods for six ball-point pen inks. Microchemical Journal, v. 138, p. 550–561, 2018. DOI: 10.21577/0100-4042.20170308

DÍAZ-SANTANA, Francisco; VEGA-MORENO, Daura; CONDE-HARDISSON, Oscar. Gas chromatography-mass spectrometry and high-performance liquid chromatography-diode array detection for dating of paper ink. Journal of Chromatography A, v. 1515, p. 187–195, 2017. DOI: 10.1016/j.chroma.2017.07.093.

EZCURRA Magdalena; GRÁVALOS, Goyo R. Análise Forense de Documentos – Instrumentos de Escrita Manual e suas Tintas: Volume I. 1 edição. São Paulo: Millenium Editora, 2012.

EZCURRA Magdalena. et al. Analytical methods for dating modern writing instrument inks on paper. Forensic Science International, v. 197, p.1-20, 2010. DOI: 10.1016/j.forsciint.2009.11.013

FERREIRA, Márcia Miguel Castro. Quimiometria: Conceitos, Métodos e Aplicações. 1ª Edição. São Paulo: Editora Unicamp, 2015.

FERREIRA, Priscila da Silva; et al. Forensic analysis of ballpoint pen inks using paper spray mass spectrometry. Analyst, v. 140, p. 811-819, 2015. DOI:10.1039/c4an01617c

GALLIDABINO, Matteo; WEYERMANN, Celine; MARQUIS, Raymond. Differentiation of blue ballpoint pen inks by positive and negative mode LDI-MS. Forensic Science International, v. 204, p. 169-178, 2011.DOI: 10.1016/j.forsciint.2010.05.027

GORZIZA, Roberta Petry et al. Chemometric Approaches in Questioned Documents. Brazilian Journal of Analytical Chemistry. Pre-publication – Accepted after peer review. DOI: 10.30744/brjac.2179-3425.RV-32-2021

GORZIZA, Roberta Petry. et al. Blue Ballpoint Pen Inks Differentiation using Multivariate Image Analysis of Digital Images Captured with PhotoMetrix PRO®. Brazilian Journal of Forensic Science, Medical Law & Bioethics, v. 9(3), p. 331-355, 2020. DOI: 10.17063/bjfs9(3)y2020331

GORZIZA, Roberta Petry. et al. Blue and Black Ballpoint Pen Inks: a Systematic Review for Ink Characterization and Dating Analysis. Brazilian Journal of Forensic Science, Medical Law & Bioethics, v. 8(3), p. 113-138, 2019. DOI: https://doi.org/10.17063/bjfs8(3)y2019113

HELFER, Gilson A. et al. Chemostat, um Software Gratuito para Análise Exploratória de Dados Multivariados. Química Nova, v. 38, n. 4, p. 575-579, 2015. DOI: 10.5935%2F0100-4042.20150063

HOFFMAN, Edmond; STROOBANT, Vincent. Mass Spectrometry Principles and Applications. 3ª Edição. Inglaterra: John Wiley and Sons Ltd, 2007.

HOSU, Anamaria; POP, Bianca; CIMPOIU, Claudia. The Forensic Analysis of Pigments from Some Inks by HPTLC. Journal of Liquid Chromatography & Related Technologies, v. 38, p. 1109–1112, 2015. DOI: 10.1080/10826076.2015.1028289

ISMAIL, Dzulkiflee; AUSTAD, Zulkefli; DESA, Wan Nur Syuhaila Desaa. Ultra-Violet and Visible (UV-VIS) Spectroscopy and Chemometrics Techniques for Forensic Analysis of Ballpoint Pen Inks: A Preliminary Study. Malaysian Journal of Forensic Sciences, v. 5, p. 47-52, 2014.

JONES, Roger W.; MCCLELLAND, John F. Analysis of Writing Inks on Paper Using Direct Analysis in Real Time Mass Spectrometry. Forensic Science International, v. 231, p. 1-15, 2013. DOI: 10.1016/j.forsciint.2013.04.016.

KOENIG, Àgnes; WEYERMANN, Celine. Ink Dating, Part I: Statistical Distribution of Selected Ageing Parameters in a Ballpoint Inks Reference Population. Science and Justice, v. 58, n. 1, p. 17–30, 2018. DOI: 10.1016/j.scijus.2017.08.002

KOENIG, Àgnes; MAGNOLON, Sophie; WEYERMANN, Celine. A comparative study of ballpoint ink ageing parameters using GC/MS. Forensic Science International, v. 252, p. 93–106, 2015. DOI: 10.1016/j.forsciint.2015.03.027

KULA, Agnieszka. et al. Application of laser induced breakdown spectroscopy to examination of writing inks for forensic purposes. Science and Justice, v. 54, p. 118-125, 2014. DOI: 10.1016/j.scijus.2013.09.008

KUMAR, Raj; SHARMA, Vishal. Chemometrics in Forensic Science. Trends in Analytical Chemistry, v. 105, p. 191-201, 2018. DOI: 10.1016/j.trac.2018.05.010

ORTIZ-HERRERO, Laura. et al. DATUVINK pilot study: A potential non-invasive methodology for dating ballpoint pen inks using multivariate chemometrics based on their UV–vis-NIR reflectance spectra. Microchemical Journal, v. 140, p. 158-166, 2018. DOI: 10.1016/j.microc.2018.04.019

PAVIA, Donald; LAMPMAN, Gary; KRIZ, George. Introduction to Spectroscopy: a guide for students of organic chemistry. 3ª Edição. Estados Unidos: Thomson Learning Inc., 2001.

LALLI, Priscila M. et al. Fingerprinting and aging of ink by easy ambient sonic-spray ionization mass spectrometry. Analyst, v. 135(4), p. 745-750, 2010. doi: 10.1039/b923398a

MARTINS, Angélica Rocha. et al. Determination of chronological order of crossed lines of ballpoint pens by hyperspectral image in the visible region and multivariate analysis. Forensic Science Internacional, v. 296, p. 91–100, 2019. DOI: 10.1016/j.forsciint.2019.01.021.

ROMAN, I. San. et al. DATINK pilot study: An effective methodology for ballpoint pen ink dating in questioned documents. Analytica Chimica Acta, v. 892, p. 105-114, 2015. DOI: 10.1016/j.aca.2015.08.038.

SAVIELLO, Daniela. et al. Raman Spectroscopy and Surface Enhanced Raman Scattering (SERS) for the Analysis of Blue and Black Writing Inks: Identification of Dye Content and Degradation Processes. Frontiers in Chemistry, v. 7, p. 727, 2019. DOI: 10.3389/fchem.2019.00727

SHARMA Vishal; KUMAR, Raj. Fourier transform infrared spectroscopy and high-performance thin layer chromatography for characterization and multivariate discrimination of blue ballpoint pen ink for forensic applications. Vibrational Spectroscopy, v. 92, p. 96–104, 2017. DOI: 10.1016/j.vibspec.2017.05.006

SILVA, Carolina; et al. Chemometric approaches for document dating: Handling paper variability. Analytica Chimica Acta, v. 1031, p. 28-37, 2018. DOI: 10.1016/j.aca.2018.06.031

SILVA, Veronica. et al. Non-destructive identification of different types and brands of blue pen inks in cursive handwriting by visible spectroscopy and PLS-DA for forensic analysis. Microchemical Journal, v. 116, p. 235-243, 2014. DOI: 10.5935/0103-5053.20140140

WEYERMANN, Celine. et al. Evaluation of the Photodegradation of Crystal Violet upon Light Exposure by Mass Spectrometric and Spectroscopic Methods. Journal of Forensic Science, v. 54(2), p. 339-345, 2009. DOI: 10.1111/j.1556-4029.2008.00975.x

WEYERMANN, Celine; SPENGLER, Berhardnt. The potential of artificial aging for modeling of natural aging processes of ballpoint ink. Forensic Science International, v. 180, p.23-31, 2008. DOI: 10.1016/j.forsciint.2008.06.012

WEYERMANN, Celine; SCHIFFER, Beatrice; MARGOT, Pierre. A logical framework to ballpoint ink dating interpretation. Science and Justice, v. 48, p. 118–125, 2008. DOI: 10.1016/j.scijus.2007.10.009.

WILLIAMS, Mary. et al. Analysis of black writing ink by electrospray ionization mass spectrometry. Forensic Science International, v. 191, p. 97-103, 2009. DOI: 10.1016/j.forsciint.2009.07.003

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