Elemental analysis of glass and ink by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser induced breakdown spectroscopy (LIBS)

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, μXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

Evaluation of the evidential value of the elemental composition of glass, ink and paper by laser-based microspectrochemical methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87–100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling's T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Ink Under the Fingernails: Making Print in Nineteenth-Century Mexico City

This dissertation examines Mexico City’s material politics of print—the central actors engaged in making print, their activities and relationships, and the legal, business, and social dimensions of production—across the nineteenth century. Inside urban printshops, a socially diverse group of men ranging from manual laborers to educated editors collaborated to make the printed items that fueled political debates and partisan struggles in the new republic. By investigating how print was produced, regulated, and consumed, this dissertation argues that printers shaped some of the most pressing conflicts that marked Mexico’s first formative century: over freedom of expression, the role of religion in government, and the emergence of liberalism. Printers shaped debates not only because they issued texts that fueled elite politics but precisely because they operated at the nexus where new liberal guarantees like freedom of the press and intellectual property intersected with politics and patronage, the regulatory efforts of the emerging state, and the harsh realities of a post-colonial economy.

Historians of Mexico have typically approached print as a vehicle for texts written by elites, which they argue contributed to the development of a national public sphere or print culture in spite of low literacy levels. By shifting the focus to print’s production, my work instead reveals that a range of urban residents—from prominent printshop owners to government ministers to street vendors—produced, engaged, and deployed printed items in contests unfolding in the urban environment. As print increasingly functioned as a political weapon in the decades after independence, print production itself became an arena in struggles over the emerging contours of politics and state formation, even as printing technologies remained relatively unchanged over time.

This work examines previously unexplored archival documents, including official correspondence, legal cases, business transactions, and printshop labor records, to shed new light on Mexico City printers’ interactions with the emerging national government, and reveal the degree to which heated ideological debates emerged intertwined with the most basic concerns over the tangible practices of print. By delving into the rich social and cultural world of printing—described by intellectuals and workers alike in memoirs, fiction, caricatures and periodicals— it also considers how printers’ particular status straddling elite and working worlds led them to challenge boundaries drawn by elites that separated manual and intellectual labors. Finally, this study engages the full range of printed documents made in Mexico City printshops not just as texts but also as objects with particular visual and material qualities whose uses and meanings were shaped not only by emergent republicanism but also by powerful colonial legacies that generated ambivalent attitudes towards print’s transformative power.

Elemental Analysis of Glass and Ink by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Laser Induced Breakdown Spectroscopy (LIBS)

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, µXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

Correlation between the photocatalysed oxidation of methylene blue in solution and the reduction of resazurin in a photocatalyst activity indicator ink (Rz Paii)

Assessment of Activity of 'Transparent and Clear' and 'Opaque and Highly Coloured' Photocatalytic Samples using a Fluorescent Photocatalytic Activity Indicator Ink, FPaii.

The photocatalytic activity of self-cleaning glass is assessed using a resazurin (Rz) photocatalyst activity indicator ink, i.e. Rz paii, via both the rate of change in the colour of the ink (blue to pink), R(Abs), and the rate of change in the fluorescence intensity, R(Fl), (λ(excitation) = 593 nm; λ(emission) = 639 nm) of the ink. In both cases the kinetics are zero order. Additional work with a range of glass samples of different photocatalytic activity reveal R(Abs) is directly related to R(Fl), thereby showing that the latter, like the former, can be used to provide a measure of the photocatalytic activity of the sample under test. The measured value of R(Fl) is found to be the same for 5 pieces of, otherwise identical, selfcleaning glass with: black, red, blue, yellow and no coloured tape stuck to their backs, which demonstrates that R(Fl) measurements can be used to measure photocatalytic activity under conditions of high colour and opacity under which R(Abs) cannot be measured. The relevance of this novel, fluorescence-based paii to the assessment of the activity of highly coloured, opaque photocatalytic samples, such as paints and tiles, is discussed briefly.

Comparing reading processes on e-ink displays and print

E-book reading devices open new possibilities in the field of reading. More activities than just reading a book can be performed with a single electronic device. For a long time, electronic reading devices have not been favored because their active LCD displays used to have a relatively low contrast. The new generation of electronic reading devices differs from earlier ones in the nature of the display: active LCD displays have been replaced with displays based on e-ink technology, which has display properties closer to that of printed paper. Moreover, e-ink technology has higher power efficiency, thereby increasing battery life and reducing weight. At first sight, the display looks similar to paper print, but the question remains whether the reading behavior also is equal to that of reading a printed book. In the present study, we analyzed and compared reading behavior on e-reader displays and on printed paper. The results suggest that the reading behavior on e-readers is indeed very similar to the reading behavior on print. Participants shared similar proportions of regressive saccades while reading on e-readers and print. Significant differences in fixation duration suggest that e-readers, in some situations, may even provide better legibility.