Analzying questioned documents in a nondestructive nature has been an issue for the forensic science community. Using nondestructive techniques such as video spectral comparator does not give reliable information due to the variations in gray or color levels that are distinguished differently by analysts. Destructive techniques such as chromatography give dependable, qualitative and quantitative, information but involves altering the evidentiary value of these questioned documents. The paradox of document examination becomes a problem when document evidence is involved, especially when trying to preserve its evidentiary value and critical data is needed. Thus, a nondestructive technique has been developed to solve the loopholes in document examinations. Direct analyte-probed nanoextraction (DAPNe) is a nanomanipulation technique that extracts ink directly off the document for further examination. A watermark is left, at most, post-extraction. DAPNe utilizes a tip emitter, pre-filled with a solvent, which is controlled in x-, y-, and z-coordinates via joystick controller and aspirates/extracts using a pressure injector. The versatility of this technique lies within the solvent chemistry and its capability to be coupled to various types of instrumentation. The extraction solvent can be altered to target specific components in the ink. For example, a chelator may be added to target metal ions found in ancient inks or methanol may be added to target certain organic resins and binding agents found in modern inks. In this study, DAPNe has been coupled to nanospray ionization mass spectrometry, fluorescence microscopy, Raman spectroscopy, matrix-assisted laser desorption ionization mass spectrometry, and laser ablation to solve questioned document concerns in the area of falsified or forged documents, redacted documents, and aging studies.

Improvements in printing technology and the wide accessibility of advanced printers has resulted in an increase in counterfeiting. Of particular interest to forensic document examiners, ink analysis of security documents has emerged as an important tool for the analysis, comparison, and association of inks to a potential production source. In this study, methods were developed for Py-GC/MS, ATR-FTIR, DART-MS, and MALDI-MS analyses of printing inks of four classes: 78 inkjet inks, 76 toners, 79 offset inks, and 86 intaglio inks in order to generate information on the organic chemical characterization of the inks to determine the ability to associate and discriminate the inks for uses in security document examinations. The suite of analytical techniques evaluated in the study focused on having the following analytical characteristics: 1) rapid analysis time, 2) little-to-no sample preparation, 3) minimal destructiveness to the sample, 4) allow for association of inks with the same source of origin as well as discrimination of inks originating from different sources. As a result of this study, a novel searchable library database of inks was developed for use with each analytical chemical method that allows for data fusion. Py-GC/MS analysis was used to achieve >63% discrimination of toner inks on the basis of the characterization of polymer degradation products. The combination of a protocol implementing first ATR-FTIR and subsequently DART-MS analysis resulted in >96% discrimination for toners, 95% for inkjet, >92% for offset, and >54% for intaglio. In addition, a case study was performed using DART-MS to illustrate its utility as a tool for ink analysis in document examination. The results of MALDI-MS analyses from two different instruments resulted in >90% discrimination of a subset of all inks by characterizing the colorant molecules present in ink formulations. A study characterizing luminescent compounds present in the formulation of inks in crossed-line intersections was performed using a combination of MALDI-MS, LC-MS, and TLC. Overall, it was shown that the combination of analytical techniques included within this dissertation can provide information on the organic chemical composition of four classes of printing inks, which is useful for the future of document examination.

An optimized method of extraction, an instrumental analysis method and data analysis was proposed for black writing inks based on direct infusion electrospray-mass spectrometry (ESI-MS). The sampling and analysis method is both minimally destructive and able to assess differences in inks from a reference collection of thirty ballpoint, gel, and rollerball inks. The methanol extracts of ink on paper samples were analyzed with three direct infusion (ESI-MS) methods. Each method varied scan voltage negative and positive, ESI fragmentor applied voltage (+120V, +0V, and -120V), and mobile phase additive. Direct infusion ESI-MS analysis, followed by pair-wise comparisons of the observed ion data in binary form allowed inks to be distinguished from each other. The photobleaching of the dye Basic Violet 3 (BV3) in ink-onpaper samples was examined to determine the use of degradation products as a marker of the age of the writing sample. The extent of photobleaching of BV3 was determined using several illumination sources. Pair-wise comparison of observed ion data was able to distinguish 29 of 30 ink samples using the combined three instrumental methods. Out of 435 pair-wise comparisons 429 pairs could be discriminated from each other using the combined three methods. This is a 98.6% discrimination with the combined analysis scheme