FORENSIC APPLICATIONS OF LA-ICP-MS: ELEMENTAL PROFILING AND EVALUATION OF HOMOGENEITY IN SODA-LIME...
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FORENSIC APPLICATIONS FORENSIC APPLICATIONS OF LA-ICP-MS: ELEMENTAL OF LA-ICP-MS: ELEMENTAL
PROFILING AND PROFILING AND EVALUATION OF EVALUATION OF
HOMOGENEITY IN SODA-HOMOGENEITY IN SODA-LIME CONTAINER GLASSLIME CONTAINER GLASS
Karen J. Harrington
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Inductively Coupled Plasma Inductively Coupled Plasma Mass Spectrometry (ICP-MS)Mass Spectrometry (ICP-MS)
Previous method of RI predominantly used Elemental analysis research began three decades
ago Allows classification of product type and use Shown to be a discriminating technique for forensic analysis
Drawbacks Dangerous digestions Sample size requirements Destructive nature
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Laser ablation (LA)-ICP-MSLaser ablation (LA)-ICP-MSA viable method for forensic glass
comparisonsCreates aerosol of super-fine glass
fragments– Advantages
Decreased sample prep. time Minimal sample consumption Maintains good sensitivity for most elements Less risk of contamination
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HomogeneityHomogeneityAre elements consistent within a glass item
(micro-homogeneity)?– Natural heterogeneity (result of manufacturing)
Contamination, natural variation in raw material
How do elements vary between glass items?– Variation beyond natural fluctuation?
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Previous Research on Previous Research on HomogeneityHomogeneity
– LA-ICP-MS does reveal small natural variations in glass
– Understanding homogeneity within a unit of glass is a factor when:
Comparing samples from same categorical sources Comparing samples from different manufacturers
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HomogeneityHomogeneity
Glass items typically maintain some homogeneity overall
Glass of the same type can often be distinguished on an item-item basis
Glass bottles tend to be more variable and may not be distinguishable from each other within one manufacturer
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Project GoalsProject Goals
How consistent are elemental profiles in glass bottles?
What are appropriate match-criteria to balance false positives and false negatives?
How variable are glass bottles within a manufacturer?
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Background – Stage IBackground – Stage I
Verify valid set of match-criteria– Examine homogeneity of a single bottle– Determine what criteria allow for treatment of
bottle as a whole unit
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Background – Stage IIBackground – Stage II
Determine normal/natural manufacturer variability– Hourly runs– Daily runs– Simultaneous/daily for multiple furnaces
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Method – Sample SelectionMethod – Sample Selection
Gallo Glass Company, Modesto, CA Typical soda-lime, with cullet (25% recycled) Stage 1
– 10 bottles from two furnaces, variable time intervals, colors, types (3 fragments each from neck, sidewall, base regions of each bottle)
Stage 2– Hourly, daily, daily simultaneous furnace
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Method – Analyte SelectionMethod – Analyte Selection
Analytes were selected from an acid digestion of selected bottles from the population.
Ratios were determined based on %RSD and mass-to-charge values.
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Method – Comparison CriteriaMethod – Comparison Criteria
T-tests and ANOVA were found to be unacceptable for the purposes of this project.
Typical case-work match-criteria of ±2 SD was used
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Method – InstrumentationMethod – InstrumentationPerkin-Elmer ELAN DRC II ICP-MS (a)New Wave Research Nd: YAG LA (1 =
213nm) unit (b)
a, b Dodds, A.J., Land, D.P., Pollock, E.M. Determination of Elemental Homogeneity in Automotive Windshields by LA-ICP-MS. The CACNews. 4th Quarter 2005. 17 – 20.
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10 comparisons of multiple regions showed indistinguishable elemental profiles for 13 ratios with ± 2SD.
When ± 3SD was applied to Sr/Zr and Fe/Cr (the two consistently problematic ratios), all 10 bottles showed indistinguishable elemental profiles for 15 ratios.
Results – Stage IResults – Stage I
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Results – Stage IResults – Stage IComparison Areas Distinguishable
Elemental ProfilesIndistinguishable elemental profiles
Inside Neck vs. Sidewall Inside Sidewall vs. Base Inside Base vs. Neck Outside Neck vs. Sidewall Outside Sidewall vs. Base Outside Base vs. Neck Neck vs. Sidewall, all Sidewall vs. Base, all Base vs. Neck, all Inside vs. Outside
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Results – Stage IResults – Stage IComparison Areas Distinguishable
Elemental ProfilesIndistinguishable elemental profiles
Inside Neck vs. Sidewall Inside Sidewall vs. Base Inside Base vs. Neck Outside Neck vs. Sidewall Outside Sidewall vs. Base Outside Base vs. Neck Neck vs. Sidewall, all Sidewall vs. Base, all Base vs. Neck, all Inside vs. Outside
Inside Neck vs. Sidewall, Ca/Mn
0.0
1000.0
2000.0
3000.0
4000.0
5000.0
#1 #11
#23
#29
#34
#47
#58
#59
#70
#148
Sample #
Con
cent
ratio
n
Mean (iN)Mean (iS)
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Results – Stage IResults – Stage IComparison Areas Distinguishable
Elemental ProfilesIndistinguishable elemental profiles
Inside Neck vs. Sidewall Inside Sidewall vs. Base Inside Base vs. Neck Outside Neck vs. Sidewall Outside Sidewall vs. Base Outside Base vs. Neck Neck vs. Sidewall, all Sidewall vs. Base, all Base vs. Neck, all Inside vs. Outside
Neck vs. Sidewall, Ca/Mn
0.01000.02000.03000.04000.05000.06000.0
Sample #
Con
cent
ratio
n
Mean (N)Mean (S)
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Results – Stage IResults – Stage IComparison Areas Distinguishable
Elemental ProfilesIndistinguishable elemental profiles
Inside Neck vs. Sidewall Inside Sidewall vs. Base Inside Base vs. Neck Outside Neck vs. Sidewall Outside Sidewall vs. Base Outside Base vs. Neck Neck vs. Sidewall, all Sidewall vs. Base, all Base vs. Neck, all Inside vs. Outside
Inside vs. Outside, Ca/Mn
0.0
1000.02000.0
3000.04000.0
5000.0
Sample #
Con
cent
ratio
n
Mean (i)Mean (o)
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Results – Stage 2 Results – Stage 2 (hourly)(hourly)
Comparison Areas Distinguishable Elemental Profiles
Indistinguishable elemental profiles
Group 1 – furnace 3 *Group 2 – furnace 2 *Group 1 vs. Group 2
* Group 1 (one bottle distinguishable for 1 ratio) and Group 2 (two bottles distinguishable for 3 ratios) show some distinguishable elemental profiles from other bottles.
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Results – Stage 2 Results – Stage 2 (hourly)(hourly)
Comparison Areas Distinguishable Elemental Profiles
Indistinguishable elemental profiles
Group 1 – furnace 3 *Group 2 – furnace 2 *Group 1 vs. Group 2
* Group 1 (bottle # 38 for 1 element) and Group 2 (bottles #48 and #50 for 3 elements) show some distinguishable elemental profiles from other bottles.
Table 3 – Relative Discrimination Capabilities ±2 SD (±3 SD for Sr/Zr and Fe/Cr)Numbers in parenthesis = ±3SD (±4SD for Sr/Zr and Fe/Cr)
Number of Samples: 12/group (66 comparisons) No. of distinguishable pairs
Elemental RatiosSr/ZrNa/AlCa/MnZn/RbFe/CrBa/PbNi/VTi/LiCa/NdSn/LaMg/CuAs/YHf/ThSb/PrU/Ta
Group 10 (0)8 (4)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)
Group 26 (0)0 (0)1 (0)1 (0)0 (0)5 (2)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)
Group 1 vs. Group 20 (0)0 (0)1 (1)1 (1)1 (1)1 (1)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)1 (0)0 (0)
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Results – Stage 2 Results – Stage 2 (daily)(daily)
Comparison Areas Distinguishable Elemental Profiles
Indistinguishable elemental profiles
Group 3 – 7/19/05 – 7/30/05 (after 5 days) *
Group 4 – 7/31/05 – 8/15/05 (after 8 days)Group 5 – 8/9/05 – 8/21/05 (after 4 days)
* 1 bottle was indistinguishable from another that was manufactured 11 days later
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Results – Stage 2 Results – Stage 2 (daily)(daily)
Comparison Areas
Distinguishable Elemental Profiles
Indistinguishable elemental profiles
Group 3 – 7/19/05 –
7/30/05
(5 days*)
Group 4 – 7/31/05 – 8/15/05
(8 days)
Group 5 – 8/9/05 – 8/21/05
(4 days)
* 1 bottle was only distinguishable from others that were 11 days or more apart.
Table 4 – Relative Discrimination Capabilities ±2 SD (±3 SD for Sr/Zr and Fe/Cr)Numbers in parenthesis = ±3SD (±4SD for Sr/Zr and Fe/Cr)
Number of Samples: 12/group (66 comparisons) No. of distinguishable pairs
Elemental RatiosSr/ZrNa/AlCa/MnZn/RbFe/CrBa/PbNi/VTi/LiCa/NdSn/LaMg/CuAs/YHf/ThSb/PrU/Ta
Group 330 (21)
5 (1)3 (0)
15 (1)0 (0)
22 (14)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)0 (0)
Group 41 (0)0 (0)1 (0)
33 (21)0 (0)
17 (10)0 (0)0 (0)0 (0)0 (0)0 (0)8 (0)1 (0)0 (0)0 (0)
Group 52 (1)0 (0)
14 (5)50 (40)
1 (0)34 (23)
0 (0)0 (0)0 (0)0 (0)0 (0)
19 (5)0 (0)
16 (6)0 (0)
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Results – Stage 2 Results – Stage 2 (simultaneous daily)(simultaneous daily)
Comparison Areas Distinguishable Elemental Profiles
Indistinguishable elemental profiles
Furnace 1 vs. Furnace 2 Furnace 2 vs. Furnace 3 Furnace 3 vs. Furnace 1 Furnace 1 vs. Furnace 1 Furnace 2 vs. Furnace 2 Furnace 3 vs. Furnace 3
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Results – Stage 2 Results – Stage 2 (simultaneous daily)(simultaneous daily)Table 5 – Relative Discrimination Capabilities ±2 SD (±3 SD for Sr/Zr and Fe/Cr)
Numbers in parenthesis = ±3SD (±4SD for Sr/Zr and Fe/Cr)Number of Samples: 6 (15 comparisons) No. of distinguishable pairs
Elemental RatiosSr/ZrNa/AlCa/MnZn/RbFe/CrBa/PbNi/VTi/LiCa/NdSn/LaMg/CuAs/YHf/ThSb/PrU/Ta
Group 60 (0)0 (0)
13 (12)15 (12)12 (12)13 (12)
0 (0)8 (4)0 (0)8 (6)8 (8)2 (0)0 (0)
11 (8)0 (0)
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Conclusion - hourlyConclusion - hourly
Bottles manufactured from the same furnace are typically not distinguishable when compared hourly
80 – 90% of bottles manufactured within a daily production lot from the same furnace share indistinguishable elemental profiles
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Conclusion - dailyConclusion - daily
Bottles manufactured from the same furnace between 4 and 8 days apart (11 maximum) are typically distinguishable.
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Conclusion – simultaneous Conclusion – simultaneous dailydaily
Bottles manufactured at the same time from different furnaces are distinguishable.
Additionally, some bottles manufactured at
the same time on two consecutive days from the same furnace may be distinguishable.
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Conclusion – significant Conclusion – significant informationinformation
Supports previous research– Same case/six-pack are indistinguishable 1
– Indistinguishable profiles are typically from same manufacturer 2
Gallo Glass Company – Produces 800 cases/hour– 1 billion bottles per year
1 Trejos, T and Almirall, J.R. Sampling strategies for the analysis of glass fragments by LA-ICP-MS Part I. Micro-homogeneity study of glass and its application to the interpretation of forensic evidence. Talanta. 67(2) 388 – 395 (August 2005).
2 J.R. Almirall. Glass as evidence of association. In Mute Witness; When Trace Evidence Makes the Case, M. Houck (Ed.), Academic Press, San Diego, CA, USE, 139-155 (2001).
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Final ConclusionsFinal Conclusions
Still important to collect/examine multiple fragments from question sample 1
Provides evidentiary value to forensic examinations– Can distinguish between furnaces of same
manufacturer– Can distinguish between bottles from the same
furnace after approximately 8-11 days1 Trejos, T and Almirall, J.R. Sampling strategies for the analysis of glass fragments by LA-ICP-MS Part I. Micro-homogeneity study of glass and its application to the interpretation of forensic evidence. Talanta. 67(2) 388 – 395 (August 2005).
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Future ResearchFuture Research
Multiple manufacturer studies
Bottle distribution (cases, vendors)
More effective statistical studies
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AcknowledgmentsAcknowledgments
Sacramento County District Attorney Laboratory of Forensic Services and Staff
Gallo Glass CompanyUniversity of California, Davis: Forensic
Science Masters programCalifornia Criminalistics Institute