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Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS

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Abstract

Elemental analysis of glass was conducted by 16 forensic science laboratories, providing a direct comparison between three analytical methods [micro-x-ray fluorescence spectroscopy (μ-XRF), solution analysis using inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma mass spectrometry]. Interlaboratory studies using glass standard reference materials and other glass samples were designed to (a) evaluate the analytical performance between different laboratories using the same method, (b) evaluate the analytical performance of the different methods, (c) evaluate the capabilities of the methods to correctly associate glass that originated from the same source and to correctly discriminate glass samples that do not share the same source, and (d) standardize the methods of analysis and interpretation of results. Reference materials NIST 612, NIST 1831, FGS 1, and FGS 2 were employed to cross-validate these sensitive techniques and to optimize and standardize the analytical protocols. The resulting figures of merit for the ICP-MS methods include repeatability better than 5 % RSD, reproducibility between laboratories better than 10 % RSD, bias better than 10 %, and limits of detection between 0.03 and 9 μg g−1 for the majority of the elements monitored. The figures of merit for the μ-XRF methods include repeatability better than 11 % RSD, reproducibility between laboratories after normalization of the data better than 16 % RSD, and limits of detection between 5.8 and 7,400 μg g−1. The results from this study also compare the analytical performance of different forensic science laboratories conducting elemental analysis of glass evidence fragments using the three analytical methods.

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References

  1. Almirall JR, Buckleton J, Curran JM, Hicks TN (2000) In: Curran JM, Champod TNH, Buckleton JS (eds) Forensic interpretation of glass evidence examination of glass. CRC Press, Boca Raton, FL

    Google Scholar 

  2. Reeve V, Mathiesen J, Fong W (1976) Elemental analysis by energy dispersive X-ray: a significant factor in the forensic analysis of glass. J Forensic Sci 21:291–306

    CAS  Google Scholar 

  3. Dudley RJ, Howden CR, Taylor TJ, Smalldon KW (1980) The discrimination and classification of small fragments of window and non-window glasses using energy-dispersive X-ray fluorescence spectrometry. X-Ray Spectrom 9:119–122

    Article  CAS  Google Scholar 

  4. Howden CR, Dudley RJ, Smalldon KW (1978) The analysis of small glass fragments using energy dispersive x-ray fluorescence spectrometry. J Forensic Sci Soc 18:99–112

    Article  CAS  Google Scholar 

  5. Koons RD, Peters CA, Rebbert PS (1991) Comparison of refractive index, energy dispersive X-ray fluorescence and inductively coupled plasma atomic emission spectrometry for forensic characterization of sheet glass fragments. J Anal At Spectrom 6:451–456

    Article  CAS  Google Scholar 

  6. Hicks T, Monard Sermier F, Goldmann T, Brunelle A, Champod C, Margot P (2003) The classification and discrimination of glass fragments using nondestructive energy dispersive X-ray μ fluorescence. Forensic Sci Int 137:107–118

    Article  CAS  Google Scholar 

  7. Andrasko J, Machly A (1978) The discrimination between samples of window glass by combining physical and chemical techniques. J Forensic Sci 22:250–262

    Google Scholar 

  8. Becker S, Gunaratman L, Hicks T, Stoecklein W, Warman G (2001) The differentiation of float glass using refractive index and elemental analysis: comparisons of techniques. Problems of Foren Sci 47:80–92

    CAS  Google Scholar 

  9. Duckworth DC, Morton SJ, Bayne K, Montero S, Koons RD, Almirall JR (2002) Forensic glass analysis by ICP-MS: a multi-element assessment of discriminating power via analysis of variance and pairwise comparisons. J Anal At Spectrom 17:662–668

    Article  CAS  Google Scholar 

  10. Koons RD, Fiedler C, Rawalt C (1988) Classification and discrimination of sheet and container glasses by inductively coupled plasma atomic emission spectrometry and pattern recognition. J Forensic Sci 33:49–67

    CAS  Google Scholar 

  11. Montero S, Hobbs A, French T, Almirall JR (2003) Elemental analysis of glass fragments by ICP-MS as evidence of association: analysis of a case. J Forensic Sci 48:1101–1107

    CAS  Google Scholar 

  12. Almirall JR, Trejos T (2006) Advances in forensic analysis of glass fragments with a focus on refractive index and elemental analysis. Forensic Sci Rev 18(2):74–96

    Google Scholar 

  13. Suzuki Y, Sugita R, Suzuki S, Marumo Y (2000) Forensic discrimination of bottle glass by refractive index measurement and analysis of trace elements with ICP-MS. Anal Sci 16:1195–1198

    Article  CAS  Google Scholar 

  14. Hughes JC, Catterick T, Southear G (1976) The quantitative analysis of glass by atomic absorption spectroscopy. J Forensic Sci 8:217–227

    Article  CAS  Google Scholar 

  15. Coleman RF, Goode GC (1973) Comparison of glass fragments by neutron activation analysis. J Radiol Chem 15:367–372

    Article  CAS  Google Scholar 

  16. Koons RD, Buscaglia J (2001) Distribution of refractive index values in sheet glasses, Forensic Science Commun 3,1 http://www.fbi.gov/about-us/lab/forensic-science-communications/fsc/jan2001/koons.htm. Accessed 3 April 2013

  17. Catterick T, Hickman DA (1981) The quantitative analysis of glass by inductively coupled plasma-atomic-emission spectrometry: a five-element survey. Forensic Sci Int 17:253–263

    Article  CAS  Google Scholar 

  18. Buscaglia J (1994) Elemental analysis of small glass fragments in forensic science. Anal Chim Acta 288:17–24

    Article  CAS  Google Scholar 

  19. Ryland S (2011) Discrimination of flat (sheet) glass specimens having similar refractive indices using micro X-ray fluorescence spectrometry. J Am Soc Trace Evid Examiners 2(1):2–12

    Google Scholar 

  20. Committee on Identifying the Needs of the Forensic Sciences Community, National Research Council (2009) Strengthening forensic science in the United States: a path forward. The National Academies Press, Washington DC

  21. Brozel-Mucha Z, Zadora G (1998) Differentiating between various types of glass using SEM-EDX elemental analysis: a preliminary study. Problems of Foren Sci 37:68–89

    Google Scholar 

  22. Kuisma-Kursula P (2000) Accuracy, precision and detection limits of SEM-WDS, SEM-EDS and PIXE in the multi-elemental analysis of medieval glass. X-Ray Spectrom 29:111–118

    Article  CAS  Google Scholar 

  23. Krüsemann H (2001) SEMs and forensic science. Probl Forensic Sci XLVII:110–121

    Google Scholar 

  24. Roedel TC, Bronk H, Haschke M (2003) Investigation of the influence of particle size on the quantitative analysis of glasses by energy-dispersive micro x-ray fluorescence spectrometry. X-Ray Spectrom 31:16–26

    Article  Google Scholar 

  25. Ryland S (1986) Sheet or container? Forensic glass comparisons with an emphasis on source classification. J Forensic Sci 31:1314–1329

    CAS  Google Scholar 

  26. Naes B, Umpierrez S, Ryland SG, Barnett C, Almirall JR (2008) A comparison of laser ablation inductively coupled plasma mass spectrometry, micro X-ray fluorescence spectroscopy, and laser induced breakdown spectroscopy for the discrimination of automotive glass. Spectrochim Acta Part B 63(10):1145–1150

    Article  Google Scholar 

  27. Wolnik KL, Gaston CM, Fricke FL (1989) Analysis of glass in product tampering investigations by ICP-AES with a hydrofluoric acid resistant torch. J Anal At Spectrom 4:27–31

    Article  CAS  Google Scholar 

  28. Moenke-Blankenburg L, Schumann T, Günther D, Kuss HM, Paul M (1992) Quantitative analysis of glass using ICP-AES and ICP-MS, laser micro-analysis ICP-AES and laser ablation ICP-MS. J Anal At Spectrom 7:251–254

    Article  CAS  Google Scholar 

  29. Zurhaar A, Mullings L (1990) Characterization of forensic glass samples using inductively coupled mass spectrometry. J Anal At Spectrom 5:611–617

    Article  CAS  Google Scholar 

  30. Parouchais T, Warner IM, Palmer LT, Kobus H (1996) The analysis of small glass fragments using inductively coupled plasma mass spectrometry. J Forensic Sci 41:351–360

    CAS  Google Scholar 

  31. Duckworth DC, Bayne CK, Morton SJ, Almirall JR (2000) Analysis of variance of forensic glass analysis by ICP-MS: variance within the method. J Anal At Spectrom 15:821–828

    Article  CAS  Google Scholar 

  32. Imbert JL, Telouck P (1993) Application of laser ablation ICP-MS to elemental analysis of glasses. Microchim Acta 110:151–160

    Article  CAS  Google Scholar 

  33. Trejos T, Almirall JR (2005) Sampling strategies for the analysis of glass fragments by LA-ICPMS. Part I. Microhomogeneity study of glass and its application to the interpretation of forensic evidence. Talanta 67:388–395

    Article  CAS  Google Scholar 

  34. Trejos T, Almirall JR (2005) Sampling strategies for the analysis of glass fragments by LA-ICPMS. Part II. Sample size and shape considerations. Talanta 67:396–401

    Article  CAS  Google Scholar 

  35. Trejos T, Montero S, Almirall JR (2003) Analysis and comparison of glass fragments by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and ICP-MS). Anal Bioanal Chem 376(8):1255–1264

    Article  CAS  Google Scholar 

  36. Latkoczy C, Dücking M, Becker S et al (2005) Evaluation of a standard method for the quantitative elemental analysis of float glass samples by LA-ICP-MS. J Forensic Sci 50:1327–1341

    Article  CAS  Google Scholar 

  37. Becker S, Watzke P, Dücking M, Stoecklein W (2003) Laser ablation in forensic glass analysis: the use of matrix matched standards for quantitative float glass analysis. Forensic Sci Int 136(1):361

    Google Scholar 

  38. Almirall JR, Trejos T, Hobbs A, Furton K (2003) In: Carapezza EM (ed), Elemental analysis of glass and paint samples of forensic interest by ICP-MS using laser ablation solid sample introduction, Sensors, and Command, Control, Communications, and Intelligence (C3I) Technologies for Homeland Defense and Law Enforcement II. Proc Int Soc Opt Eng (SPIE) (SPIE) 5071:193–196

  39. Bajic S, Aeschliman D, Staetveit NJ, Baldwin DP, Houk RS (2005) Analysis of glass fragments by laser ablation-inductively coupled plasma-mass spectrometry and principal component analysis. J Forensic Sci 50:1123–1127

    Article  CAS  Google Scholar 

  40. Berends-Montero S, Wiarda W, de Joode P, van der Peijl G (2006) Forensic analysis of float glass using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS): validation of a method. J Anal At Spectrom 21:1185–1193

    Article  CAS  Google Scholar 

  41. American Society for Testing and Materials Method E2330-04 (2004) Standard test method for determination of trace elements in glass using inductively couple plasma mass spectrometry (ICP-MS). In: ASTM Annual Book of ASTM Standards, 14.02. American Society for Testing and Materials, West Conshohocken

  42. Pearce NJ, Perkins WT, Westgate JA, Gorton MP, Jackson SE, Neal CR (1996) A compilation of new and published major and trace element data for NIST SRM 610 and NIST SRM 612 glass reference materials. Geostandard Newsletter 1:115–144

    Google Scholar 

  43. American Society for Testing and Materials ASTM Practice E177 (2004) Standard practice for the use of the terms precision and bias in ASTM methods. American Society for Testing and Materials, West Conshohocken

    Google Scholar 

  44. International Organization for Standardization ISO 3534–1 (2006) Statistics—vocabulary and symbols—part 1: general statistical terms and terms used in probability. ISO, Geneva, Switzerland

    Google Scholar 

  45. International Organization for Standardization ISO 5725–2 (1994) Accuracy (trueness and precision) of measurement methods and results, part 2: basic methods for the determination of repeatability and reproducibility of a standard measurement method. ISO, Geneva, Switzerland

    Google Scholar 

  46. EURACHEM/CITAC Guide CG4 (2000) Quantifying uncertainty in analytical measurements, Ellison SLR, Rosslein M, Williams A (eds), EURACHEM/CITAC, UK

  47. Castro W, Trejos T, Naes B, Almirall JR (2008) Comparison of high resolution and dynamic reaction cell ICP-MS capabilities for the forensic analysis of iron in glass. Anal Bioanal Chem 392:663–672

    Article  CAS  Google Scholar 

  48. Miller JN, Miller JC (2000) Statistics and chemometrics for analytical chemistry, 4th edn. Pearson Education Limited, Harlow, England

    Google Scholar 

  49. ACS Committee on Environmental Improvement (1980) Guidelines for data acquisition and data quality evaluation in environmental chemistry. Analytical Chemistry 52:2242–2249

  50. International Union of Pure and Applied Chemistry (IUPAC) (1976) Commission on Spectrochemical and Other Optical Procedures for Analysis. Pure Appl Chem 45:99–103

    Article  Google Scholar 

  51. Ernst T, Berman T, Buscaglia J et al. (2012) Signal to noise ratios in forensic glass analysis by micro x-ray fluorescence spectrometry. Journal of XRay Spectrom. doi: 10.1002/xrs.2437

  52. Weis P, Dücking M, Watzke P, Menges S, Becker S (2011) Establishing a match criterion in forensic comparison analysis of float glass using laser ablation inductively coupled plasma mass spectrometry. J Anal At Spectrom 26:1273–1284

    Article  CAS  Google Scholar 

  53. American Society for Testing and Materials ASTM (2012, WK39818) Standard test method for the determination of trace elements in soda-lime glass fragments using laser ablation inductively coupled plasma mass spectrometry for forensic comparisons

  54. American Society for Testing and Materials ASTM (2012, WK39817) Standard test method for forensic comparison of glass using micro x-ray fluorescence (μ-XRF) spectrometry

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Acknowledgments

This project was supported by Award No. 2010-DN-BX-K179 from the National Institute of Justice, Office of Justice Programs, U.S. Department of Justice. The opinions, findings, and conclusions or recommendations expressed in this presentation are those of the authors and do not necessarily reflect those of the Department of Justice, the Department of the Army or the Department of Defense. Thanks to all of the Elemental Analysis Working Group members and their agencies for devoting the time necessary to complete this project. This is publication number 12–14 of the FBI Laboratory Division. Names of commercial manufacturers are provided for identification purposes only, and inclusion does not imply endorsement of the manufacturer, or its products or services by the FBI. The views expressed are those of the authors and do not necessarily reflect the official policy or position of the FBI or the U.S. Government.

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Authors and Affiliations

  1. International Forensic Research Institute, Florida International University, OE116 11200 SW 8th St, Miami, FL, 33199, USA

    Tatiana Trejos, Anamary Tarifa & Jose Almirall

  2. Federal Bureau of Investigation, Laboratory Division, Counterterrorism and Forensic Science Research Unit, 2501 Investigation Parkway, Quantico, VA, 22135, USA

    Robert Koons & JoAnn Buscaglia

  3. Bundeskriminalamt (BKA), Forensic Science Institute, 65173, Wiesbaden, Germany

    Stefan Becker, Marc Duecking & Peter Weis

  4. Florida Department of Law Enforcement, Orlando Regional Operations Center, 500 W. Robinson St., Orlando, FL, 32801, USA

    Ted Berman & Scott Ryland

  5. US Army Criminal Investigation Laboratory, 4930 N 31st St, Forest Park, GA, 30297-5202, USA

    Tiffany Eckert-Lumsdon & Kim Mooney

  6. Michigan State Police-Grand Rapids Laboratory, 720 Fuller Ave NE, Grand Rapids, MI, 49503, USA

    Troy Ernst

  7. Miami Dade Police Department, Forensic Science Services Bureau, 91105 NW 25th St, Miami, FL, 33172, USA

    Christopher Hanlon

  8. Center of Forensic Sciences, 25 Grosvenor St, Toronto, ON, Canada, M7A268

    Alex Heydon & David Rudell

  9. Tennessee Bureau of Investigation, Forensic Services Division, 901 R.S Gass Blvd, Nashville, TN, 37216, USA

    Randall Nelson

  10. Johnson County Sheriff’s Office Crime Laboratory, 11890 S., Sunset Olathe, KS, 66061, USA

    Kristine Olsson

  11. Microtrace LLC, 790 Fletcher Drive, Elgin, IL, 60123, USA

    Christopher Palenik

  12. Sacramento County District Attorney’s Office, Laboratory of Forensic Services, 4800 Broadway, Sacramento, CA, 95820, USA

    Edward Chip Pollock

  13. Texas Department of Public Safety Crime Laboratory, 5800 Guadalupe, Austin, TX, 78752, USA

    Melissa Valadez

  14. Department of Chemistry and Biochemistry, Florida International University, OE116 11200 SW 8th St, Miami, FL, 33199, USA

    Jose Almirall

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  1. Tatiana Trejos
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  2. Robert Koons
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  3. Stefan Becker
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  4. Ted Berman
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  5. JoAnn Buscaglia
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  6. Marc Duecking
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  7. Tiffany Eckert-Lumsdon
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  8. Troy Ernst
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  9. Christopher Hanlon
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  10. Alex Heydon
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  11. Kim Mooney
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  12. Randall Nelson
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  13. Kristine Olsson
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  14. Christopher Palenik
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  15. Edward Chip Pollock
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  16. David Rudell
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  17. Scott Ryland
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  18. Anamary Tarifa
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  19. Melissa Valadez
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  20. Peter Weis
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  21. Jose Almirall
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Correspondence to Jose Almirall.

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Trejos, T., Koons, R., Becker, S. et al. Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS. Anal Bioanal Chem 405, 5393–5409 (2013). https://doi.org/10.1007/s00216-013-6978-y

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  • DOI: https://doi.org/10.1007/s00216-013-6978-y

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