Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis
Abstract
In the realm of forensic science and materials analysis, understanding the composition and characteristics of everyday materials can unveil a plethora of information. This study leverages the precision and efficiency of Laser-Induced Plasma Spectroscopy (LIBS) to dive deep into the elemental makeup of A-4 paper across different brands, offering applications beyond academic research. The results can offer a valuable reference in forensic investigations where distinguishing between paper types could provide key evidence in document authentication or fraud cases. Furthermore, the method provides insights for quality control in paper manufacturing by identifying unique elemental markers that can verify the origin and consistency of paper products. This innovative research employed the ECCO®² brand Laser-Induced Breakdown Spectroscopy (LIBS) device, a state-of-the-art spectrometric system. The device was used to analyze samples from seven distinct A4 paper brands: Mopak®, Office International Copier Bond®, Double A®, Excellent Copy Paper®, Gold®, Master®, and Vera®. Controlled via a computer system and specialized ECCO®² software, the ECCO®² facilitated a comprehensive elemental analysis of these paper samples, focusing on the presence of specific inorganic materials such as glass, inks, and toners that hold forensic value. The study meticulously selected 11 elements (K, Sr, Si, Na, Ba, Mg, Ca, C, Al, Fe, and Ti) for elemental data analysis, based on their relevance and potential to reveal the composition and source of the materials. These elements were chosen due to their prevalence in common additives, fillers, and bleaching agents used in paper manufacturing, making them effective markers for differentiating paper brands based on elemental composition. The LIBS technique, a non-contact and rapid analytical method, allowed for the precise detection of these elements without the need for sample preparation, showcasing its practicality in forensic and analytical applications.
Through Principal Component Analysis (PCA), 76.65% discrimination was initially achieved among the A4 paper samples. Notably, when three elements (Al, Fe, and Ti) were excluded, discrimination increased to 83.78%. Further analyses using Principal Component Analysis (PCA) on peak height and peak area data from A4 paper samples yielded discrimination rates of 80.916% and 85.947%, respectively. In this context, peak height refers to the maximum intensity of each elemental emission line, while peak area represents the integrated area under each spectral peak. These distinct spectral metrics capture different aspects of the elemental composition of A4 paper samples, enhancing PCA’s ability to effectively distinguish between paper brands. Finally, when PCA was performed using six elemental pairs identified by the ECCO®² device as optimal for A4 paper differentiation, the discrimination rate reached 97.313%, with variation values calculated at approximately 80%. These results underscore the LIBS method’s reliability and precision in distinguishing different paper types, affirming its valuable application for forensic and quality control purposes.
Keywords
Project Number
1
References
- [1] Brunelle, R.L., Crawford, K.R., “Advances in the Forensic Analysis and Dating of Writing Ink”, Charles C Thomas Publisher (2003).
- [2] Shaffer, D.K., “Forensic Document Analysis Using Scanning Microscopy”, Proc. SPIE 7378 (2009) : 73782E1-73782E11.
- [3] Kelly, J.S., Lindblom, B., “Scientific Examination of Questioned Documents”, Taylor and Francis (2006).
- [4] Spence, L.D., Baker, A.T., Byrne, J.P., “Characterization of Document Paper Using Elemental Compositions Determined by Inductively Coupled Plasma Mass Spectrometry”, Journal of Analytical Atomic Spectrometry 15 (2000) : 813-819.
- [5] Trejos, T., Flores, A., Almirall, J.R., “Micro-Spectrochemical Analysis of Document Paper and Gel Inks by Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Laser-Induced Breakdown Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 65 (2010) : 884-895.
- [6] Pessanha, S., Manso, M., Guilherme, A., Costa, M., Carvalho, M.L., “Investigation of Historical Documents for Forensic Purposes by X-Ray Fluorescence Spectrometry”, Surface and Interface Analysis 42 (2010) : 419-422.
- [7] Sarkar, A., Aggarwal, S.K., Alamelu, D., “Laser-Induced Breakdown Spectroscopy for Rapid Identification of Different Types of Paper for Forensic Application”, Analytical Methods 2 (2010) : 32-36.
- [8] Kaminska, A., Sawczak, M., Komar, K., Sliwinski, G., “Application of Laser Ablation for Conservation of Historical Paper Documents”, Applied Surface Science 253 (2007) : 7860-7864.
- [9] Lennard, C., El-Deftar, M.M., Robertson, J., “Forensic Application of Laser-Induced Breakdown Spectroscopy for the Discrimination of Questioned Documents”, Forensic Science International 254 (2015) : 68-79.
- [10] Häkkänen, H., Houni, J., Kaski, S., Korppi-Tommola, J.E.I., “Analysis of Paper by Laser-Induced Plasma Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) : 737-742.
- [11] Oujja, M., Vila, A., Rebollar, E., García, J.F., Castillejo, M., “Identification of Inks and Structural Characterization of Contemporary Artistic Prints by Laser-Induced Breakdown Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 60 (2005) : 1140-1148.
- [12] Metzinger, A., Rajkó, R., Galbács, G., “Discrimination of Paper and Print Types Based on Their Laser-Induced Breakdown Spectra”, Spectrochimica Acta Part B: Atomic Spectroscopy 94–95 (2014) : 48-57.
- [13] Almeida, M.R., Correa, D.N., Rocha, W.F.C., Scafi, F.J.O., Poppi, R.J., “Discrimination Between Authentic and Counterfeit Banknotes Using Raman Spectroscopy and PLS-DA with Uncertainty Estimation”, Microchemical Journal 109 (2013) : 170-177.
- [14] Body, D., Chadwick, B.L., “Optimization of the Spectral Data Processing in a LIBS Simultaneous Elemental Analysis System”, Spectrochimica Acta Part B: Atomic Spectroscopy 56(6) (2001) : 725-736.
- [15] Buehlmann, S., “Paper Discrimination Using ICP-MS & LA-ICP-MS,” University of Technology, Sydney, Australia (2012).
Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis
Abstract
In the realm of forensic science and materials analysis, understanding the composition and characteristics of everyday materials can unveil a plethora of information. This study leverages the precision and efficiency of Laser-Induced Plasma Spectroscopy (LIBS) to dive deep into the elemental makeup of A-4 paper across different brands, offering applications beyond academic research. The results can offer a valuable reference in forensic investigations where distinguishing between paper types could provide key evidence in document authentication or fraud cases. Furthermore, the method provides insights for quality control in paper manufacturing by identifying unique elemental markers that can verify the origin and consistency of paper products. This innovative research employed the ECCO®² brand Laser-Induced Breakdown Spectroscopy (LIBS) device, a state-of-the-art spectrometric system. The device was used to analyze samples from seven distinct A4 paper brands: Mopak®, Office International Copier Bond®, Double A®, Excellent Copy Paper®, Gold®, Master®, and Vera®. Controlled via a computer system and specialized ECCO®² software, the ECCO®² facilitated a comprehensive elemental analysis of these paper samples, focusing on the presence of specific inorganic materials such as glass, inks, and toners that hold forensic value. The study meticulously selected 11 elements (K, Sr, Si, Na, Ba, Mg, Ca, C, Al, Fe, and Ti) for elemental data analysis, based on their relevance and potential to reveal the composition and source of the materials. These elements were chosen due to their prevalence in common additives, fillers, and bleaching agents used in paper manufacturing, making them effective markers for differentiating paper brands based on elemental composition. The LIBS technique, a non-contact and rapid analytical method, allowed for the precise detection of these elements without the need for sample preparation, showcasing its practicality in forensic and analytical applications.
Through Principal Component Analysis (PCA), 76.65% discrimination was initially achieved among the A4 paper samples. Notably, when three elements (Al, Fe, and Ti) were excluded, discrimination increased to 83.78%. Further analyses using Principal Component Analysis (PCA) on peak height and peak area data from A4 paper samples yielded discrimination rates of 80.916% and 85.947%, respectively. In this context, peak height refers to the maximum intensity of each elemental emission line, while peak area represents the integrated area under each spectral peak. These distinct spectral metrics capture different aspects of the elemental composition of A4 paper samples, enhancing PCA’s ability to effectively distinguish between paper brands. Finally, when PCA was performed using six elemental pairs identified by the ECCO®² device as optimal for A4 paper differentiation, the discrimination rate reached 97.313%, with variation values calculated at approximately 80%. These results underscore the LIBS method’s reliability and precision in distinguishing different paper types, affirming its valuable application for forensic and quality control purposes.
Keywords
Ethical Statement
Ethical Statement We, the authors, hereby declare that the research presented in the manuscript titled "Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis," adheres to the ethical standards and guidelines established by the Journal of Engineering Technology and Applied Sciences and relevant professional and institutional codes of conduct. 1. Authorship and Contributions: All listed authors have made significant contributions to the conception, design, execution, and interpretation of the study. All authors have reviewed and approved the final manuscript. 2. Originality and Plagiarism: This manuscript is our original work and has not been published elsewhere in any form. We have appropriately cited and acknowledged the work of others, and the manuscript does not contain any form of plagiarism. 3. Data Integrity and Transparency: The data presented in this study have been accurately recorded and analyzed. We ensure that all raw data and related materials are available and can be provided upon request for verification and replication of the results. 4. Conflict of Interest: The authors declare no conflict of interest with any individual or organization that could have influenced the research presented in this manuscript. Any funding sources and sponsors have been disclosed in the manuscript. 5. Ethical Approval: As the research involved the analysis of non-biological materials (A-4 paper), it did not require approval from an institutional review board or ethics committee. No human or animal subjects were involved in this study. 6. Funding and Support: Any financial support and sponsorship for this research have been acknowledged in the manuscript. The sponsors had no role in the study design, data collection and analysis, decision to publish, or preparation of the manuscript. 7. Confidentiality and Privacy: We have ensured that any information that could potentially identify individuals or institutions involved in the study has been anonymized or omitted to maintain confidentiality and privacy. By submitting this manuscript, we agree to abide by the ethical guidelines of the Journal of Engineering Technology and Applied Sciences and accept responsibility for maintaining the integrity and transparency of our research. Sincerely, Ines Arbi University of Carthage, Laboratory of Materials Physics, Surface Spectrometer CommonService Unit, Faculty of Sciences of Bizerte, Jarzouna, 7021 Bizerte, Tunisia. Dr Yunus Yürekli Council of Forensic Medicine, Istanbul, Turkiye Hülya Özen Topkapı Istanbul University Istanbul, Turkiye.
Supporting Institution
We, the authors, conducted the research presented in the manuscript titled "Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis" independently, without the direct support of an institution.
Project Number
1
Thanks
We, the authors, would like to express our sincere gratitude to the individuals and entities that contributed to the completion of our research titled "Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis." We would like to express our deepest gratitude to Professor Doctor Erol Kam for their invaluable guidance and support throughout the research and preparation of our manuscript titled "Distinguishing Brands of A-4 Paper Through Elemental Analysis Using Laser-Induced Breakdown Spectroscopy and Principal Component Analysis. Also He Provided crucial guidance on the application of Laser-Induced Breakdown Spectroscopy (LIBS) and Principal Component Analysis (PCA), which were key to our research methodology and data analysis. We also wish to thank our families and friends for their unwavering support and encouragement throughout the research and writing process. The collaborative efforts and support of these individuals and groups were crucial to our success. Sincerely, Ines Arbi University of Carthage, Laboratory of Materials Physics, Surface Spectrometer CommonService Unit, Faculty of Sciences of Bizerte, Jarzouna, 7021 Bizerte, Tunisia. Dr Yunus Yürekli Council of Forensic Medicine, Istanbul, Turkiye Dr.Hülya Özen Topkapı Istanbul University Istanbul, Turkiye.
References
- [1] Brunelle, R.L., Crawford, K.R., “Advances in the Forensic Analysis and Dating of Writing Ink”, Charles C Thomas Publisher (2003).
- [2] Shaffer, D.K., “Forensic Document Analysis Using Scanning Microscopy”, Proc. SPIE 7378 (2009) : 73782E1-73782E11.
- [3] Kelly, J.S., Lindblom, B., “Scientific Examination of Questioned Documents”, Taylor and Francis (2006).
- [4] Spence, L.D., Baker, A.T., Byrne, J.P., “Characterization of Document Paper Using Elemental Compositions Determined by Inductively Coupled Plasma Mass Spectrometry”, Journal of Analytical Atomic Spectrometry 15 (2000) : 813-819.
- [5] Trejos, T., Flores, A., Almirall, J.R., “Micro-Spectrochemical Analysis of Document Paper and Gel Inks by Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Laser-Induced Breakdown Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 65 (2010) : 884-895.
- [6] Pessanha, S., Manso, M., Guilherme, A., Costa, M., Carvalho, M.L., “Investigation of Historical Documents for Forensic Purposes by X-Ray Fluorescence Spectrometry”, Surface and Interface Analysis 42 (2010) : 419-422.
- [7] Sarkar, A., Aggarwal, S.K., Alamelu, D., “Laser-Induced Breakdown Spectroscopy for Rapid Identification of Different Types of Paper for Forensic Application”, Analytical Methods 2 (2010) : 32-36.
- [8] Kaminska, A., Sawczak, M., Komar, K., Sliwinski, G., “Application of Laser Ablation for Conservation of Historical Paper Documents”, Applied Surface Science 253 (2007) : 7860-7864.
- [9] Lennard, C., El-Deftar, M.M., Robertson, J., “Forensic Application of Laser-Induced Breakdown Spectroscopy for the Discrimination of Questioned Documents”, Forensic Science International 254 (2015) : 68-79.
- [10] Häkkänen, H., Houni, J., Kaski, S., Korppi-Tommola, J.E.I., “Analysis of Paper by Laser-Induced Plasma Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) : 737-742.
- [11] Oujja, M., Vila, A., Rebollar, E., García, J.F., Castillejo, M., “Identification of Inks and Structural Characterization of Contemporary Artistic Prints by Laser-Induced Breakdown Spectroscopy”, Spectrochimica Acta Part B: Atomic Spectroscopy 60 (2005) : 1140-1148.
- [12] Metzinger, A., Rajkó, R., Galbács, G., “Discrimination of Paper and Print Types Based on Their Laser-Induced Breakdown Spectra”, Spectrochimica Acta Part B: Atomic Spectroscopy 94–95 (2014) : 48-57.
- [13] Almeida, M.R., Correa, D.N., Rocha, W.F.C., Scafi, F.J.O., Poppi, R.J., “Discrimination Between Authentic and Counterfeit Banknotes Using Raman Spectroscopy and PLS-DA with Uncertainty Estimation”, Microchemical Journal 109 (2013) : 170-177.
- [14] Body, D., Chadwick, B.L., “Optimization of the Spectral Data Processing in a LIBS Simultaneous Elemental Analysis System”, Spectrochimica Acta Part B: Atomic Spectroscopy 56(6) (2001) : 725-736.
- [15] Buehlmann, S., “Paper Discrimination Using ICP-MS & LA-ICP-MS,” University of Technology, Sydney, Australia (2012).
Details
| Primary Language | English |
|---|---|
| Subjects | Digital Forensics, Electronic, Optics and Magnetic Materials |
| Journal Section | Research Article |
| Authors | |
| Project Number | 1 |
| Publication Date | December 31, 2024 |
| Submission Date | July 23, 2024 |
| Acceptance Date | October 29, 2024 |
| Published in Issue | Year 2024 Volume: 9 Issue: 3 |