agilent technologies at tiaft 2013 · 2016-09-03 · agilent technologies at tiaft 2013 analytical...
TRANSCRIPT
Agilent Technologies
at TIAFT 2013
Analytical approaches for the
measurement of trace metals
in forensic samples
Funchal, Madeira
September 2- 6
Introduction: Areas of Interest in Forensic Analysis C
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• Identification and evaluation of physical evidence including arson & accelerants analysis, bulk drug identification, and trace analysis.
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• Identification of drugs & chemicals in bodily fluids for workplace drug testing, doping control/sports medicine, driving under the influence testing, and death investigation.
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• Identification of an individual(s) or their remains using genetic samples.
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• Analysis & comparation of handwriting, paper ink, etc, to verify authenticity.
Agilent Elemental Analysis Portfolio
4100 MP-AES
ICP-OES
Atomic Absorption
AAS
GFAA
ICP-MS
Nuevo
Nuevo
Introduction: What is ICP-MS?
ICP - Inductively Coupled Plasma
• high temperature electrical discharge, which decomposes, atomizes and ionizes samples
– forms ions, so compounds not measured
MS - Mass Spectrometer
• quadrupole (“quad”) mass analyzer
• mass range from 5 to 260 amu (Li to U...)
– separates all elements in rapid sequential scan
– isotopic information available
• ions measured using dual mode detector
– ppt level LODs for most elements
– Calibration range up to 1000’s ppm
• Interferences removed using collision/reaction cell
An inorganic (elemental) analysis technique
Which Elements can be Measured Using ICP-MS?
All elements in colour can be measured –
only those elements present in the plasma
gas, those <5 amu, >260amu, and those
which are not ionized, are inaccessible
Key Requirements for Forensic Elemental Analysis
• allows many different types of samples to be analyzed
• measure many elements in the same acquisition • “fingerprinting”
• freedom from molecular interference
Flexible Sample Introduction
• allows the analysis of trace species
• often provide good “fingerprint” Good Detection Limits
• allows analysis of trace to ppm levels Wide dynamic range
Meeting the Requirements: Agilent 7700x ICP-MS
High matrix
introduction
(HMI) dilution
gas inlet
Peltier-cooled
spray chamber
Off-axis ion lens
Low-flow
Sample
Introduction
Fast, frequency-
matching 27MHz RF
generator
High-
performance
vacuum system
Cell gas inlet
High-frequency
hyperbolic
quadruple
Fast,
simultaneous
dual mode
detector (9 orders
dynamic range)
High-transmission,
matrix tolerant
interface
3rd generation Octopole
Reaction System (ORS3)
Agilent 7700x ICP-MS:
The Three Key Performance Benefits
1. Matrix Tolerance – Sample Intro/Plasma/HMI
2. Interference Removal – He Mode
3. Dynamic Range – 9 Orders at the Detector
Expanding our capabilities: Agilent 8800 ICP-QQQ
World’s first Triple Quadrupole ICP-MS (ICP-QQQ)
New modes of operation and performance not possible with quadrupole ICP-MS
Joins the Agilent 7700, the highest performing quadrupole ICP-MS system
Unique capabilities, based on proven technology
Agilent 7700
Single-quad (ICP-
QMS)
New Agilent
8800 ICP-QQQ
Agilent 8800 ICP-QQQ: How Does it Work?
ICP (plasma) and Interface:
Forms and extracts ions from
the sample (just like the 7700)
EM (detector): Measures the ions
that are scanned by Q2 (just like the
7700)
Q1 – controls ions that
enter the cell
• Consistent reactions
even if sample
composition changes
ORS3 – collision/ reaction
gas added
• Ions react and are
neutralized or moved
• Product ions are formed
Q2 – selects the target
analyte mass
• Interference-free analyte
ions passed to EM
Some examples of Forensic Applications with
ICPMS
Criminalistic
Gunshot Residue (GSR) Analysis
Using Lase Ablation: Glass Fragment Analysis, Adhesive Tape and Paint Chip Analysis, Analysis of Bic Black Pen Ink, Analysis of a Single Hair, Synthetic Fibers
Toxicology
Drug Testing. Using Impurities to Characterize Drugs of Abuse
Post-mortem. Heavy metal poisoning, As toxicity and speciation, occupational exposure
Applications typically run at specialized clinical labs (Biological Samples)
Gunshot Residue (GSR) Analysis by ICPMS (I)
• Firing a gun produces a "plume" of gas that is
dispersed in all directions and condensed into
individual particles. Traces of the explosive
material is deposit on their hands
• It is a tool for the interpretation of the criminal
event. Ex link the weapon to the user
Gunshot Residue (GSR) particles can be determined by the identification of
lead, antimony and barium, together with additional information provided by
copper, zinc and iron.
GSR samples collected from hands of an individual
• fired a 9mm semiautomatic gun two-handed,
• samples were collected approximately 40 minutes after the shooting.
Sample Prep: GSR samples and calibration solutions were placed on Q-tip cotton
swabs
• a pair of swabs for each sample and standard
• placed in 15-mL polypropylene screw-top tubes and dried overnight
Gunshot Residue (GSR) Analysis by ICPMS (II)
Sample 121Sb (µg) 138Ba (µg) 208Pb (µg)
Left palm 1.26 4.09 5.33
Bottom of left hand 0.27 0.91 1.50
Right Palm 2.20 8.18 11.1
Bottom of right palm 0.12 0.40 0.91
Swab blank 0.007 <0.001 <0.001
Laser Ablation Coupled to ICPMS (I)
• Forensic scientist has interest in determine the origin of any material
found in the scene of a crime – can help to link this material to a suspect.
• But, due to the great variety, shape, sizes of samples, there is a need for a
flexible analytical tool capable of analyze the trace element content of
solid samples directly.
LA-ICP-MS:
Can identify, compare and discriminate
elemental and isotopes differences at
ppb level
Laser Ablation Coupled to ICPMS (II)
Principles of LA-ICP-MS
• The sample surface is irradiated with deep-
UV (213 nm) output from laser source
• The high-intensity pulsed ultraviolet (UV)
beam is focused onto the sample surface in
an ablation chamber or cell, which is purged
with argon.
• The resultant aerosol is transported to the
ICP in an argon carrier gas stream where it is
decomposed, atomized and ionized
Microdestructive technique: less than 1 ug of the sample is ablated and
the essential integrity of the sample is maintained
LA-ICP-MS: Glass Fragment Analysis (I)
Glass samples can be analyzed using simple
screening scan (qualitative or semi-quantitative)
or calibrated against well-characterized
reference glasses. NIST 600 series Trace
Elements in Glass – eg NIST 612 = 50ppm
Almost any solid fragment collected from a suspect individual or location may be
suitable for analysis using laser ablation ICP-MS – sample size limit (for standard
laser ablation chamber) is about 50um diameter minimum and 50mm diameter
maximum
Images courtesy of New Wave Research
LA-ICP-MS: Glass Fragment Analysis (II)
Data courtesy of New Wave Research
Trace Element Distribution Patterns (sum to 100%) – Synthetic Glass and
Unknown Samples
Other Sample Types Analyzed by LA-ICP-MS
Glass fragments
Packing Tape
Multi-layer paints
Coatings on glass
Ink or Toner on paper
Synthetic fibers
Heavy metals in hair
Bulk polymers
Plastic bags
Images courtesy of FBI Academy
Beneficial Features of Laser Ablation ICP-MS
Applicable to virtually all solids with little or no sample preparation
Bulk analysis (raster over sample surface)
Micro feature analysis (<5 um)
Fast analysis (<5 min from sample receipt)
Surface mapping
Depth profiling
Excellent sensitivity
Biological fluids Whole blood, serum, urine, plasma
Traces elements measurements (toxic and essential ones)
in biological fluids
Samples simply diluted (10 to 20 times) with specific basic solution
containing:
• Butanol
• EDTA
• Triton X100
• Ammonia
More than 100 samples can be prepared per hour !
Biological fluids Detection limit (DL) in µg/L
Tune Step Mass Name R LD Tune Step Mass Name R LD
[NoGas] 107 Ag 0.99978 0.003 [He] 60 Ni 0.99976 0.040
[He] 27 Al 0.99970 0.539 [NoGas] 208 Pb 0.99968 0.002
[He] 75 As 0.99978 0.002 [NoGas] 105 Pd 0.99942 0.0011
[NoGas] 137 Ba 0.99982 0.007 [NoGas] 195 Pt 0.99969 0.004
[NoGas] 9 Be 0.99950 0.0006 [NoGas] 121 Sb 0.99974 0.0009
[NoGas] 209 Bi 0.99964 0.0014 [He] 78 Se 0.99994 0.007
[NoGas] 111 Cd 0.99973 0.015 [NoGas] 118 Sn 0.99980 0.0011
[He] 59 Co 0.99979 0.004 [NoGas] 88 Sr 0.99968 0.004
[He] 52 Cr 0.99942 0.014 [NoGas] 125 Te 0.99982 0.005
[He] 63 Cu 0.99981 0.012 [He] 49 Ti 0.99911 0.091
[NoGas] 201 Hg 0.99966 0.003 [NoGas] 205 Tl 0.99974 0.0010
[NoGas] 7 Li 0.99961 0.009 [NoGas] 238 U 0.99969 0.0002
[He] 55 Mn 0.99972 0.009 [He] 51 V 0.99965 0.005
[NoGas] 95 Mo 0.99982 0.002 [He] 66 Zn 0.99976 0.067
Excellent limit of detection for all the elements, with range at
the ppt (ng/L) level
Tune Step Mass Name R LD Tune Step Mass Name R LD
[NoGas] 107 Ag 0.99978 0.003 [He] 60 Ni 0.99976 0.040
[He] 27 Al 0.99970 0.539 [NoGas] 208 Pb 0.99968 0.002
[He] 75 As 0.99978 0.002 [NoGas] 105 Pd 0.99942 0.0011
[NoGas] 137 Ba 0.99982 0.007 [NoGas] 195 Pt 0.99969 0.004
[NoGas] 9 Be 0.99950 0.0006 [NoGas] 121 Sb 0.99974 0.0009
[NoGas] 209 Bi 0.99964 0.0014 [He] 78 Se 0.99994 0.007
[NoGas] 111 Cd 0.99973 0.015 [NoGas] 118 Sn 0.99980 0.0011
[He] 59 Co 0.99979 0.004 [NoGas] 88 Sr 0.99968 0.004
[He] 52 Cr 0.99942 0.014 [NoGas] 125 Te 0.99982 0.005
[He] 63 Cu 0.99981 0.012 [He] 49 Ti 0.99911 0.091
[NoGas] 201 Hg 0.99966 0.003 [NoGas] 205 Tl 0.99974 0.0010
[NoGas] 7 Li 0.99961 0.009 [NoGas] 238 U 0.99969 0.0002
[He] 55 Mn 0.99972 0.009 [He] 51 V 0.99965 0.005
[NoGas] 95 Mo 0.99982 0.002 [He] 66 Zn 0.99976 0.067
Speciation analysis
Analysis of element
species
GC-ICP-MS LC-ICP-MS
CE-ICP-MS
Why speciation analysis?
Toxic
No toxicity
?
Less toxic
As speciation analysis by LC-ICP-MS in Human
Urine
Analytical needs:
•Separation of 5 As species
•Elimination of interferences linked with ArCl:
• Separation of the Cl peak with the As species
•Detection limits 0.1 µg/L for every species
•Isocratic separation – no need for time stabilization between runs
•Long term stability
Ref.: Agilent Handbook for Arsenic speciation
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
2000
8000
12000
16000
20000
24000
28000
32000
36000
40000
44000
48000
52000
AB
AsV
AsIII
MMAA
DMAA
Cl
Certified urine: NIES CRM No.18
Certified urine : NIES CRM No.18, diluted 10 times
Retention Time / min0.0 2.0 4.0 6.0 8.0 10.0 12.0
2000
6000
10000
14000
18000
22000
26000
30000
34000
1/10 NIES No.18
1/10 NIES No.18 + 1ug/L
1/10 NIES No.18 + 5ug/L
Sig
na
l / co
un
ts
Found mg/L Found2 mg/L Recovery1 % Found3 mg/L Recovery2 %
Total As 0.137 ± 0.011
AB 0.069 ± 0.012 0.0658 0.0758 100.0 0.1164 100.5
DMAA 0.036 ± 0.009 0.0313 0.0407 98.5 0.0817 100.5
As(III) 0.0025 0.0123 98.4 0.0486 92.6
MMAA 0.0026 0.0131 104.0 0.0518 98.5
As(V) 0.0024 0.0121 97.6 0.0526 100.4
Found2: 1.0 µg/L each STD spiked 10 time dilution urine CRM
Found3: 5.0 µg/L each STD spiked 10 time dilution urine CRM
Certified Value
Summary
Forensic samples are usually challenging
– Very different matrices
– Low detection limits
ICP-MS is a very useful problem solving tool:
– In terms of performance
• very few matrix effects
• low detection limits
– ICP-MS also offers capabilities that other techniques can not
• full mass scan data with semi-quantitative analysis and elemental fingerprints
• Laser Ablation for direct analysis of solid samples, such as scene of crime debris
• hyphenated ICP-MS for toxicological studies
Summary
The 7700 ICP-MS is a fast and simple analytical technique for determination of
multiple analytes in diverse matrices
• Almost every element can be determined
• Analytical range from sub-ppt to >1000ppm
• Simple operation with complex matrices – He gas mode collision/reaction cell to
remove unknown matrix-based polyatomic interferences
Laser Ablation allows direct analysis of solid samples, such as scene of crime
debris
Easy interfacing to separation techniques for speciation analysis
Capability to measure all the biological fluids with one sample preparation step
Expand your measurement capabilities with the unique 8800 ICP-MS/MS !
Thanks for your attention!