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!