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      Combination of a Green and a Traditional Method for Estimating Relative and Absolute Ink Age: A Case Study of Ballpoint Pen Ink Dating in Vietnam

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          Abstract

          The dating of ink in questioned documents remains a significant challenge in forensic investigations in Vietnam and other countries. Many forensic examination methods have been usually applied to ensure the highest accuracy of the assessment results while maintaining high environment awareness. In this study, paper characteristics were physically tested to confirm source similarity, and the relative ink dating was established by high-performance thin-layer chromatography (HPTLC). Absolute ink dating by solvent and dye identification was performed by Raman spectrometry—a green technique, using a time-dependent degradation model for crystal violet and the comparison between 2-phenoxyethanol peak intensities. We found that the relative dating of the questioned document was 14 ± 3 months lesser than that of the reference samples, i.e., the absolute age of the questioned samples was estimated to be 24 ± 3 months. The combination of the conventional HPTLC method with the dynamic crystal violet degradation Raman model provides promising results for relative and absolute ink dating of ballpoint pens, which can be applied for documents written 1–15 years prior to the time of examination. The combination of the abovementioned methods demonstrated an acceptable error margin, affording highly practical applications in modern forensic science.

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          Green analytical methodologies.

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            Degradation pathways of crystal violet by Fenton and Fenton-like systems: condition optimization and intermediate separation and identification.

            The main advantage of Fenton's reagent (FR) over other OH systems is its simplicity. FR has the potential for widespread use in treating wastewater, but compared to other OH systems, little information on the dye degradation pathways of FR exists. The degradation of crystal violet (CV), a triphenylmethane dye, by FR was determined as a function of reagent concentration and ratio and pH in the batch treatment. The experimental results showed the optimum Fe(2+)/H(2)O(2) ratio to be 0.5mM:50mM and the optimum Fe(3+)/H(2)O(2) ratio to be 1mM:50mM. Optimal pH was about 3. To obtain a better understanding of the mechanistic details of Fenton reagent's degradation of CV dye, the intermediates of the process were separated, identified, and characterized by HPLC-PDA-ESI-MS and GC-MS techniques in this study. Indications were that the probable degradation pathways were N-de-methylation and cleavage of the conjugated chromophore structure. The intermediates were generated in the order of the reaction time and relative concentration, indicating that the N-de-methylation degradation of CV dye is a major reaction pathway. The reaction mechanisms proposed in this research should prove useful for future application of the technology to the decolorization of dyes.
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              Application of Raman Spectroscopy and Surface-Enhanced Raman Scattering to the Analysis of Synthetic Dyes Found in Ballpoint Pen Inks

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                Author and article information

                Contributors
                Journal
                J Anal Methods Chem
                J Anal Methods Chem
                jamc
                Journal of Analytical Methods in Chemistry
                Hindawi
                2090-8865
                2090-8873
                2021
                15 May 2021
                : 2021
                : 8870541
                Affiliations
                1VNU University of Science, Vietnam National University–Hanoi, 19 Le Thanh Tong St., Hoan Kiem Dist., Hanoi 100000, Vietnam
                2Center for Consultancy, Civil Assessment–67 Khuat Duy Tien St., Thanh Xuan Dist., Hanoi 100000, Vietnam
                3Institute of Forensic Science-99 Nguyen Tuan St., Thanh Xuan Dist., Hanoi 100000, Vietnam
                Author notes

                Academic Editor: Dang Quoc Thuyet

                Author information
                https://orcid.org/0000-0003-4403-3771
                https://orcid.org/0000-0002-2403-6863
                https://orcid.org/0000-0002-9401-1178
                https://orcid.org/0000-0003-1468-4821
                Article
                10.1155/2021/8870541
                8143886
                7afc539c-848c-4b29-8e12-b07d01c41a1f
                Copyright © 2021 Anh Duc Hoang et al.

                This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                : 11 September 2020
                : 2 May 2021
                Categories
                Research Article

                Analytical chemistry
                Analytical chemistry

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