Agilent Technologies at TIAFT 2013

Transcription

1 Agilent Technologies at TIAFT 2013 Analytical approaches for the measurement of trace metals in forensic samples Funchal, Madeira September 2-6

2 CRIMINALISTIC TOXICOLOGY DNA INVESTIGATION DOCUMENT EXAMINATION Introduction: Areas of Interest in Forensic Analysis Identification and evaluation of physical evidence including arson & accelerants analysis, bulk drug identification, and trace analysis. Identification of drugs & chemicals in bodily fluids for workplace drug testing, doping control/sports medicine, driving under the influence testing, and death investigation. Identification of an individual(s) or their remains using genetic samples. Analysis & comparation of handwriting, paper ink, etc, to verify authenticity.

3 Agilent Elemental Analysis Portfolio Atomic Absorption AAS 4100 MP-AES Nuevo ICP-OES GFAA ICP-MS Nuevo

4 Introduction: What is ICP-MS? An inorganic (elemental) analysis technique 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

5 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

6 Key Requirements for Forensic Elemental Analysis Flexible Sample Introduction allows many different types of samples to be analyzed measure many elements in the same acquisition fingerprinting freedom from molecular interference Good Detection Limits allows the analysis of trace species often provide good fingerprint Wide dynamic range allows analysis of trace to ppm levels

7 Meeting the Requirements: Agilent 7700x ICP-MS High matrix introduction (HMI) dilution gas inlet Low-flow Sample Introduction Peltier-cooled spray chamber Off-axis ion lens Cell gas inlet 3 rd generation Octopole Reaction System (ORS 3 ) Fast, simultaneous dual mode detector (9 orders dynamic range) High-frequency hyperbolic quadruple Fast, frequencymatching 27MHz RF generator High-transmission, matrix tolerant interface Highperformance vacuum system

8 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

9 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 New Agilent 8800 ICP-QQQ Agilent 7700 Single-quad (ICP- QMS)

10 Agilent 8800 ICP-QQQ: How Does it Work? ICP (plasma) and Interface: Forms and extracts ions from the sample (just like the 7700) Q1 controls ions that enter the cell Consistent reactions even if sample composition changes ORS 3 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 EM (detector): Measures the ions that are scanned by Q2 (just like the 7700)

11 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)

12 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.

13 Gunshot Residue (GSR) Analysis by ICPMS (II) 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 Sample 121Sb (µg) 138Ba (µg) 208Pb (µg) Left palm Bottom of left hand Right Palm Bottom of right palm Swab blank <0.001 <0.001

14 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

15 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

16 LA-ICP-MS: Glass Fragment Analysis (I) 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 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 Images courtesy of New Wave Research

17 Data courtesy of New Wave Research LA-ICP-MS: Glass Fragment Analysis (II) Trace Element Distribution Patterns (sum to 100%) Synthetic Glass and Unknown Samples

18 Images courtesy of FBI Academy 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

19 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

20 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!

21 Biological fluids Detection limit (DL) in µg/l Tune Tune Step Step Mass Mass Name Name R R LD LD Tune Tune Step Step Mass Mass Name Name R R LD LD [NoGas] Ag Ag [He] [He] Ni Ni [He] [He] Al Al [NoGas] Pb Pb [He] [He] As As [NoGas] Pd Pd [NoGas] Ba Ba [NoGas] Pt Pt [NoGas] 9 9 Be Be [NoGas] Sb Sb [NoGas] Bi Bi [He] [He] Se Se [NoGas] Cd Cd [NoGas] Sn Sn [He] [He] Co Co [NoGas] Sr Sr [He] [He] Cr Cr [NoGas] Te Te [He] [He] Cu Cu [He] [He] Ti Ti [NoGas] Hg Hg [NoGas] Tl Tl [NoGas] 7 7 Li Li [NoGas] U U [He] [He] Mn Mn [He] [He] V V [NoGas] Mo Mo [He] [He] Zn Zn Excellent limit of detection for all the elements, with range at the ppt (ng/l) level

22 Speciation analysis LC-ICP-MS GC-ICP-MS Analysis of element species CE-ICP-MS

23 Why speciation analysis? Toxic Less toxic No toxicity?

24 As speciation analysis by LC-ICP-MS in Human Urine Analytical needs: Separation of 5 As species AB Cl 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 DMAA AsIII MMAA AsV Ref.: Agilent Handbook for Arsenic speciation

25 Signal / counts Certified urine: NIES CRM No /10 NIES No /10 NIES No ug/L 1/10 NIES No ug/L Retention Time / min Certified urine : NIES CRM No.18, diluted 10 times Certified Value Found mg/l Found2 mg/l Recovery1 % Found3 mg/l Recovery2 % Total As ± AB ± DMAA ± As(III) MMAA As(V) 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

26 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

27 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!

28 Thanks for your attention!