The author(s) shown below used Federal funding provided by the U.S. Department of Justice to prepare the following resource: Document Title: Trace Metal Analysis by Laser Ablation- Inductively Coupled Plasma-Mass Spectrometry and X-Ray K-Edge Densitometry of Forensic Samples Author(s): Jonna Elizabeth Berry Document Number: 250420 Date Received: December 2016 Award Number: 2013-IJ-CX-0012 This resource has not been published by the U.S. Department of Justice. This resource is being made publically available through the Office of Justice Programs’ National Criminal Justice Reference Service. Opinions or points of view expressed are those of the author(s) and do not necessarily reflect the official position or policies of the U.S. Department of Justice. Trace metal analysis by laser ablation-inductively coupled plasma- mass spectrometry and x-ray K-edge densitometry of forensic samples by Jonna Elizabeth Berry A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Analytical Chemistry (Forensic Chemistry) Program of Study Committee: Robert S. Houk, Major Professor Emily Smith Young Jin Lee Patricia Thiel Thomas Holme Iowa State University Ames, Iowa 2015 Copyright © Jonna Elizabeth Berry, 2015. All rights reserved. This resource was prepared by the author(s) using Federal funds provided by the U.S. Department of Justice. Opinions or points of view expressed are those of the author(s) and do not necessarily reflect the official position or policies of the U.S. Department of Justice ii TABLE OF CONTENTS ABSTRACT………………………………. ............................................................. vi CHAPTER 1. GENERAL INTRODUCTION ...................................................... 1 The History of Elemental Analysis ...................................................................... 1 ICP-MS .........................................................................................................2 Trace Element Analysis in Forensics ................................................................... 3 LA-ICP-MS for Trace Element Analysis in Forensics ........................................ 5 Trace Elements in Lipsticks ........................................................................... 5 Trace Elements in Copper Wire ..................................................................... 6 Trace Element Analysis of Gunshot Residue with LA-ICP-MS .................. 7 Trace Element Analysis of Gunshot Residue with Radiography and K-Edge, X-Ray Densitometry ........................................................................ 9 Data Analysis for Comparison of Forensic Samples ........................................... 9 Dissertation Organization ................................................................................... 10 References .........................................................................................................10 CHAPTER 2. DISTINGUISHING LIPSTICK SAMPLES OF SIMILAR COLORS BY TRACE ELEMENT ANALYSIS FOR FORENSIC COMPARISONS ................................................................................ 16 Abstract .........................................................................................................16 Introduction ........................................................................................................ 16 Experimental ........................................................................................................ 19 Mass Scan of Lipsticks to Identify Elements Present .................................... 19 Homogeneity and Distinguishability of Lipsticks ...................................... 20 Data Analysis ................................................................................................. 20 Results and Discussion ........................................................................................ 21 Homogeneity of Trace Element Composition within a Lipstick Sample ...... 21 Distinguishing Lipsticks of Similar Color ................................................... 22 Conclusions ........................................................................................................ 24 This resource was prepared by the author(s) using Federal funds provided by the U.S. Department of Justice. Opinions or points of view expressed are those of the author(s) and do not necessarily reflect the official position or policies of the U.S. Department of Justice iii Acknowledgments................................................................................................ 25 References .........................................................................................................25 Figures .........................................................................................................29 Tables .........................................................................................................38 CHAPTER 3. SAMPLING AND SPATIAL HETEROGENEITY IN TRACE ELEMENTAL ANALYSIS OF COPPER WIRE FOR FORENSIC PAIRWISE COMPARISONS BY LASER ABLATION- INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY ................. 43 Abstract .........................................................................................................43 Introduction ........................................................................................................ 43 Experimental ........................................................................................................ 47 Samples ........................................................................................................ 47 LA-ICP-MS Analysis ................................................................................. 47 Sample Dissolution Analysis ......................................................................... 50 Data Analysis ................................................................................................. 51 Results and Discussion ........................................................................................ 52 Laser Ablation ................................................................................................ 52 Experiment I: Pairwise Comparison of Segments A, B, and C Between Nine Copper Strands .................................................................................... 53 Experiment I: Pairwise Comparison of Sub-Segments within an Individual Strand ........................................................................................ 54 Experiment II: Effects of Increased Sample Size on Pairwise Comparisons .................................................................................................. 55 Experiment II: Pairwise Comparison of Segments D, and E within an Individual Strand ............................................................................................ 57 Dissolution Experiments ................................................................................ 59 Conclusions ........................................................................................................ 60 Acknowledgments................................................................................................ 61 References .........................................................................................................62 Figures .........................................................................................................64 Tables .........................................................................................................70 This resource was prepared by the author(s) using Federal funds provided by the U.S. Department of Justice. Opinions or points of view expressed are those of the author(s) and do not necessarily reflect the official position or policies of the U.S. Department of Justice iv CHAPTER 4. TRACE METAL ANALYSIS OF FLY LARVAE AND PORCINE SKIN TISSUE FOR GUNSHOT RESIDUE ON DECOMPOSING PIG CARRION ....................................................................... 75 Abstract .........................................................................................................75 Introduction ........................................................................................................ 76 Experimental ........................................................................................................ 79 Winter Study ................................................................................................ 80 Summer Study ............................................................................................ 81 Analysis of Larvae Samples........................................................................... 81 Analysis of Skin Tissue Samples ................................................................... 82 Results and Discussion ........................................................................................ 83 Decomposition Observations and Wound Morphology: Winter Study ......... 83 Decomposition Observations and Wound Morphology: Summer Study ...... 84 Detection of Gunshot Residue .................................................................... 85 Winter Study: Skin Samples .......................................................................... 86 Winter Study: Larvae Samples ...................................................................... 86 Summer Study: Skin Samples ........................................................................ 87 Summer Study: Larvae Samples ...................................................................