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.

An Assessment of the Performances of Several Univariate Tests of Normality

The importance of checking the normality assumption in most statistical procedures especially parametric tests cannot be over emphasized as the validity of the inferences drawn from such procedures usually depend on the validity of this assumption. Numerous methods have been proposed by different authors over the years, some popular and frequently used, others, not so much. This study addresses the performance of eighteen of the available tests for different sample sizes, significance levels, and for a number of symmetric and asymmetric distributions by conducting a Monte-Carlo simulation. The results showed that considerable power is not achieved for symmetric distributions when sample size is less than one hundred and for such distributions, the kurtosis test is most powerful provided the distribution is leptokurtic or platykurtic. The Shapiro-Wilk test remains the most powerful test for asymmetric distributions. We conclude that different tests are suitable under different characteristics of alternative distributions.

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.

On the accuracy of nonsurvey regional input-output multipliers: An empirical study

Correct specification of the simple location quotients in regionalizing the national direct requirements table is essential to the accuracy of regional input-output multipliers. The purpose of this research is to examine the relative accuracy of these multipliers when earnings, employment, number of establishments, and payroll data specify the simple location quotients.^ For each specification type, I derive a column of total output multipliers and a column of total income multipliers. These multipliers are based on the 1987 benchmark input-output accounts of the U.S. economy and 1988-1992 state of Florida data.^ Error sign tests, and Standardized Mean Absolute Deviation (SMAD) statistics indicate that the output multiplier estimates overestimate the output multipliers published by the Department of Commerce-Bureau of Economic Analysis (BEA) for the state of Florida. In contrast, the income multiplier estimates underestimate the BEA's income multipliers. For a given multiplier type, the Spearman-rank correlation analysis shows that the multiplier estimates and the BEA multipliers have statistically different rank ordering of row elements. The above tests also find no significant different differences, both in size and ranking distributions, among the vectors of multiplier estimates. ^

On the accuracy of nonsurvey regional input-output multipliers : An empirical study

Correct specification of the simple location quotients in regionalizing the national direct requirements table is essential to the accuracy of regional input-output multipliers. The purpose of this research is to examine the relative accuracy of these multipliers when earnings, employment, number of establishments, and payroll data specify the simple location quotients. For each specification type, I derive a column of total output multipliers and a column of total income multipliers. These multipliers are based on the 1987 benchmark input-output accounts of the U.S. economy and 1988-1992 state of Florida data. Error sign tests, and Standardized Mean Absolute Deviation (SMAD) statistics indicate that the output multiplier estimates overestimate the output multipliers published by the Department of Commerce-Bureau of Economic Analysis (BEA) for the state of Florida. In contrast, the income multiplier estimates underestimate the BEA's income multipliers. For a given multiplier type, the Spearman-rank correlation analysis shows that the multiplier estimates and the BEA multipliers have statistically different rank ordering of row elements. The above tests also find no significant different differences, both in size and ranking distributions, among the vectors of multiplier estimates.