Toxic and Harmful Compounds by ICP-MS final ESAC 2008.pptamcham.dk/dl/esac/ESAC08-1.pdf ·...

ESAC Copenhagen15th April 200815th April 2008

Determination of Essential, Therapeutic and Toxic Elements and Their Compoundsand Toxic Elements and Their Compounds

in Biological Materials; Applications of ICP MS i th Cli i l L b tICP-MS in the Clinical Laboratory

Ed McCurdy, ICP-MS Specialist, Agilent Technologies Ltd

ESAC April 2008

Scope

Introduction to ICP-MS for clinical sample analysis• Requirement for elemental analysis in clinical samples• Routine trace element monitoring

f f• Analysis of toxic and harmful elements– Elemental screening, poisoning, radionuclides

T i t lli d– Toxic organometallic compoundsICP-MS analysis for the measurement of organic compounds• Identification and quantification of pesticide residues• Quantification of Chemical Warfare Agent degradation productsF i A li ti f ICP MSForensic Applications of ICP-MS• Laser Ablation ICP-MS• Direct Analysis of Elemental Distribution in Tissues

ESAC April 2008ESAC April 2008

What is ICP-MS?

ICP Inductively Coupled Plasma MS Mass Spectrometer

An inorganic (elemental) analysis techniqueICP - Inductively Coupled Plasma• high temperature electrical discharge,

which decomposes, atomizes and ionizes

MS - Mass Spectrometer• quadrupole (“quad”) mass analyzer• mass range from 5 to 260 amu (Li toc deco poses, ato es a d o es

samples– forms ions, so compounds not measured

directly

• mass range from 5 to 260 amu (Li to U...)– separates all elements in rapid

sequential scandirectly sequential scan– isotopic information available

• ions measured using dual mode detector– ppt level LODs for most elements– Calibration range up to 1000’s ppmCalibration range up to 1000 s ppm

• Spectral interferences removed using collision/reaction cell

ESAC April 2008

Agilent 7500cx ICP-MS System withCollision/Reaction Cell (CRC)Collision/Reaction Cell (CRC)

Multi-element interference removal by on-axis octopole reaction cell

Fast simultaneous dual mode detector (9 orders dynamic range)

Reaction Gas InletHigh temperature 27MHz plasma

Reaction Gas Inlet

27MHz plasma generator

Off-axis L

OctopolePlasma

Low flow sample introduction system

High frequency hyperbolic quadrupole

Lens


Elements of Interest in Easily Extractable Fluids (Urine Blood Serum Plasma)Fluids (Urine, Blood, Serum, Plasma)

Highly toxic heavy metalsHighly toxic heavy metals• As, Cd, Pb and Hg

Potentially toxic elements• Al, Sb, Ba, Be, Bi, Li, Ni, Sr and Tl

Essential elementsC C C M M S V d Z• Cr, Co, Cu, Mg. Mn, Se, V and Zn

Wid f l t b d i l diWide range of elements may be measured, including many, such as Be, As, Se, Hg, U, which are considered

“difficult” by other techniques


y q

Which Elements can be Measured Using ICP MS?ICP-MS?

All elements in colour can be measured only those elements present in the– only those elements present in the

plasma gas, <5amu, >260amu, and those which are not ionized, are inaccessible

ESAC April 2008

Analytical Needs for Inorganic Measurements in Clinical Laboratoriesin Clinical Laboratories

The technique must possess robust sample introductionThe technique must possess robust sample introduction

• To handle large sample numbers and differing matrices routinely monitored

Measurement of many elements in the same fast acquisitionMeasurement of many elements in the same fast acquisition

• Removal of interferences• Screening applications Quadrupole ICP MS can• Screening applications• Sample turnaround/productivity• Reduced cost of analysis

Quadrupole ICP-MS can meet all of these criteria

Reduced cost of analysis

Make measurements at trace levels (low detection limits) and at high concentrations in the same acquisitionq

• To reduce reruns, improve productivity and lower costs

The ability to measure element species is also provided by ICP-MSThe ability to measure element species is also provided by ICP MS

• Expands range of applications, and provides useful background research info


Collision/Reaction Cell to Remove M t i B d S t l I t fMatrix-Based Spectral Interferences

20

Ad t f C lli i /

15

(ppb

)

Cr52 Advantage of Collision/ Reaction Cell ICP-MS• Provides removal of

A C (

ArC and ClOoverlaps in15

tion

in B

lank

spectral overlaps –allows accurate trace element analysis in variable high matrix

ArC (mass 52) overlap in acetic acid matrix

overlaps in combined matrix

10

52 C

once

ntra

t

H2

He

NoGas

variable high-matrix samples

• Example shows the removal of ClO ArC

matrix

5

App

aren

t Cr5 NoGas removal of ClO, ArC

interferences in various matrix blanks

• He collision mode gives

ClO/ClOH(mass 52) overlap in HCl t i

00 1% 5% 5% HCl 1% 1% 200 200 500 Mi d

A He collision mode gives reliable removal of all polyatomic interferences regardless of the sample

HCl matrix

0.1% HNO3

5% HNO3

5% HCl 1% H2SO4

1% AcOH

200ppm Na

200ppm Ca

500ppm P

Mixed Matrix

Matrix Blank

matrix composition

ESAC April 2008

Routine Analysis of Urine – Sample Preparation and CalibrationPreparation and Calibration

Di t l i f i l f ll i 1/5 1/10 ( / )Direct analysis of urine samples following a 1/5 or 1/10 (v/v) dilution with deionized water and nitric acid• No clogging of the nebulizer• No particle deposition in the injector tube over 12 hours of analyses

Calibration using Method of Standard Additions (MSA), so matrix-matched standards• Standard addition calib is then converted to external calib and applied to

subsequent samplessubsequent samples• 5 µg/L Tb internal standard added to all sample and calibration solutions

Agilent Application Note: Rapid and reliable routine analysis of urine by Octopole Reaction Cell ICP-MS, 5989-2482EN, by Peter Heitland, Medical Laboratory Bremen, Germany


MS, 5989 2482EN, by Peter Heitland, Medical Laboratory Bremen, Germany

Measured and Certified Concentrations in Urine Reference Material Lyphochek®Urine Reference Material Lyphochek®

Element Concentration (µg/L - ppb)Lyphochek, level 1 Lyphochek, level 2yp , yp ,

Measured(n=10, external)

certified Measured(n=10, external)

certified(n 10, external) (n 10, external)

Cr 1.7 ± 0.2 1.2 ± 0.2 18.6 ± 2.6 20.2 ± 4.1Co 6.6 ± 0.7 6.9 ± 1.4 18.9 ± 1.4 19.1 ± 4.2C 24 ± 2 1 26 7 ± 5 4 45 ± 5 5 50 ± 10Cu 24 ± 2.1 26.7 ± 5.4 45 ± 5.5 50 ± 10Se 56 ± 5.3 49 ± 10 192 ± 17 187 ± 37As 65 ± 6 67 ± 14 162 ± 15 163 ± 33Cd 8.4 ± 1.1 8.6 ± 1.7 14.9 ± 1.9 15.6 ± 3.1Sb 6.9 ± 1.1 9 ± 1.8 34.8 ± 4.4 36.9 ± 7Tl 9 6 ± 0 8 9 7 ± 2 0 185 ± 17 198 ± 40Tl 9.6 ± 0.8 9.7 ± 2.0 185 ± 17 198 ± 40Pb 13.5±1.1 14.3 ± 2.9 68 ± 5 69 ± 14

Data: Medical Laboratory Bremen, Germany

ESAC April 2008

High Throughput Analysis of Blood Samples using 7500ce ICP MSusing 7500ce ICP-MS

Biomonitoring of trace elements in human blood samples - an important tool g p pfor occupational and environmental health

Goals of this study y

– Determine a high number of trace metals in blood of 130 unexposed subjects– Develop a rapid routine method for the multi-element analyses of blood usingDevelop a rapid routine method for the multi element analyses of blood using

collision/reaction cell-ICP–MS

Blood samples were collected in lithium heparin monovettes

• 500 uL of the sample was diluted with 100 uL 0.1% (v/v) Triton-X-100 solution and 500 uL of the internal standard solution

• This solution was made up to 5 mL with a 0.5% (v/v) NH4OH solution in a 10 mL polypropylene autosampler tube

More than 100 samples can be prepared in less than 1hour by one personMore than 100 samples can be prepared in less than 1hour by one person

Biomonitoring of 37 trace elements in blood samples from inhabitants of northern Germany by ICP–MS, Peter Heitland, Helmut D. Koster, Journal of Trace Elements in Medicine and Biology 20 (2006) 253–262


Heitland, Helmut D. Koster, Journal of Trace Elements in Medicine and Biology 20 (2006) 253 262

Analytical Figures of Merit for Blood Analysis

Limits of quantification q(LOQs), calculated in undiluted blood, range from 0 003 ug/L for 238U to 0 1 ug/L0.003 ug/L for 238U to 0.1 ug/L for 69Ga

Spike recoveries of 1 ug/L (10 ug/L for B, Mn and Sr; 200 ug/L for Cu and Rb) fromug/L for Cu and Rb) from single element calibration solutions are in the range g94 -111%

ESAC April 2008ESAC April 2008Data: Peter Heitland, Helmut D. Koster, Medical Laboratory Bremen, Germany

Effects of Sample Matrix on the Sample Introduction SystemIntroduction System

Photos of the interface and l i t d ti tsample introduction system

after a 90-sample run (whole blood).blood).

Both the sampler and skimmer cones show only

Sample Cone Skimmer Cone

skimmer cones show only minor matrix deposits – none at the cone tips

The standard 2.5mm injector torch used was virtually deposit-free. The blood deposits on spray chamber and the nebulizer blockchamber and the nebulizer block were removed using a sodium hypochlorite solution

ESAC April 2008Images: R. Wahlen et al., LGC Limited, UK

Screening for Toxic and Harmful Elements

Elemental Screening of 1:10 diluted Urine (with interference removal in He mode)

• Unique capability of ICP-MS to acquire a scan across the entire mass range in Screening to identify poisons (1:10 diluted urine scan)

• “Unknown” element spiked into urine sample

1 . 0 E 5

[ 1 ] S p e c t r u m N o . 1 [ 1 8 1 . 5 2 5 s e c ] : 0 0 2 S M P L . D # / T u n e # 1 [ C P S ] [ L i n e a r ] [

about 2 minutes, screening elements from 1000’s ppm to sub-ppb levels

1 . 0 E 5

[ 1 ] S p e c t r u m N o . 1 [ 1 8 1 . 5 3 1 s e c ] : 0 0 4 S M P L . D # / T u n e # 1 [ C P S ] [ L i n e a r ]

Unknown element spiked into urine sample

RbC NaMg

RbC NaMg

5 . 0 E 4

Zn

5 . 0 E 4

Zn

“Unknown” element

Ca

Li MoISr

Zn

CuLi MoISr

Zn

Cu

Ca

1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0/ 0 6 0

PbFeBr Ba

ICs

SrSb

Sn1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0/ > 0 0 2

PbFeBr Ba

ICs

SrSb

SnAsAs


1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0m / z - > 0 6 01 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 0 2 5 0 2 6 0m / z - > 0 0 2

Analysis of Toxic and Harmful ElementsScreening to identify poisons (1:10 diluted urine scan) • Confirmation (from isotopic template) of presence of Thallium (2ppb spike)

[1 ] S p e c t r u m N o .1 [ 1 7 5 .1 1 8 s e c ] : 0 0 3 S M P L .D / T u n e # 1 [C P S ] [L in e a r ]0 5 S M P L .D # /

– Can be quantified (semiquant) by reference to known concentration element– Note 210Po would also be seen in this mass region of the screening acquisition

1 .0 E 5

Alexander Litvinenko - poisoning

5 .0 E 4

T l

205Tl

210Po203Tl

1 9 4 1 9 6 1 9 8 2 0 0 2 0 2 2 0 4 2 0 6 2 0 8 2 1 0 2 1 2 2 1 4 2 1 6m /z >

P b

2 0 4

208Pb


1 9 4 1 9 6 1 9 8 2 0 0 2 0 2 2 0 4 2 0 6 2 0 8 2 1 0 2 1 2 2 1 4 2 1 6m /z - > 2 0 4

Measurement of Radionuclides

Left: Calibration for radionuclides is easily achieved at sub ng/L (ppt) levels, even with standard sample introduction (U p (used for illustration)

Scan of 1ppt 237Np standard, showing high sensitivity and low random backgroundg

Radionuclides are typically easily ionized and the spectrum is free from overlaps andfrom overlaps and backgrounds, so LOD’s in the pg/L (ppq) range are achieved

ESAC April 2008

Radionuclide Analysis – Quantification and Isotope Ratio Measurement

2.0E4

[1] Spectrum No.1 [ 115.786 sec]:10Urine.d / Tune #1 [CPS] [Linear]Isotope Ratio MeasurementVery high sensitivity and low background for 10ppt U in 1:10

238U (99.27%)

gdiluted urine

~1.2 million cps/ppb U

U

( )Natural U spike, so 235U (0.72% abundance) concentration was 72ppq

1.0E4ICP-MS also provides isotopic information, so U isotopic patterninformation, so U isotopic pattern (isotope ratio) can be used to identify source of contamination

N t l 0 72% 235U

235U (0.72%)

• Natural = 0.72% 235U • Waste depleted = 0.2 - 0.4% 235U• Pile depleted 0 6% 235U

228 229 230 231 232 233 234 235 236 237 238 239 240 241 242m/z->

• Pile depleted ~0.6% 235U• Enriched >0.72% 235U


Toxic Elemental Forms or “Species”

For many elements, the level of toxicity is highly dependent on the chemical form of the element, so separation (chromatography) is required

GC Laser Ablation

Optional

ICP-MSOptional

ConventionalDetector(s)

ESI MS

LC

– e.g. ESI-MS

1 0 0CE6 0

8 0

1 0 0

%

1 3 9 .0

1 4 4 .1

1 6 0 .11 7 4 .1 2 5 8 .9

2 7 6 .9

20000

25000

30000

35000

onse

(CP

S)

31P

123

4

56

78

910

0

2 0

4 0

72 04 36 68 00 32 64 96 28 60

2 0 3 .1

2 8 2 .1

0 5 10 15 20 25

0

5000

10000

15000

Res

po 10


7 10 13 16 20 23 26 29 32 36

m /z0 5 10 15 20 25

Time (min)

Example: LC-ICP-MS for As Speciation

Toxic! Many As species exist – theexist the inorganic As species are known to be toxic andLess-Toxic to be toxic and most organic species are

l i l h l

Less Toxic

Non-Toxic relatively harmless to humans.

The potentialThe potential toxicity of some species, such as th h i t f

?the huge variety of arsenosugars, has not yet been established.

ESAC April 2008ESAC April 2008Courtesy Ute Kohlmeyer GALAB, Germany

Chromatogram of As Standard (1.0 µg/L each)

Agilent Application Note: Routine

A new column has been developed to provide routine separation of the 5 most common As species in urine:Column G3288-80000 (4.6 x 250 mm) g pp

Analysis of Toxic Arsenic Species in Urine Using HPLC with ICP-MS, 5989-5505EN, by Tetsushi Sakai and Steven

( )Guard Column G3154-65002

Mobile Phase (Basic): Wilbur, Agilent TechnologiesMobile Phase (Basic):2 mM phosphate buffer solution (PBS)pH 11.0 adjusted with NaOH0 2 mM EDTA0.2 mM EDTA10 mM, CH3COONa3.0 mM NaNO31% ethanol

ESAC April 2008

Determination of Organo-As SpeciesUsing HPLC with ESI-MS & ICP-MSUsing HPLC with ESI-MS & ICP-MS

ESIESI--MSMSAgilent 1100Agilent 1100

ICPICP--MSMSAgilent 7500Agilent 7500 HPLCHPLC Agilent 1100Agilent 1100Agilent 7500Agilent 7500 Agilent Agilent

11001100

Elemental specific detectionElemental specific detection Molecular specific detectionMolecular specific detection

15 %15 % 85 %85 %

Single HPLC System with controlled split to provide sample flow to ESI-MS and ICP-MS. Provides simultaneous measurement of As-containing compounds and As concentration (ICP-MS) and concentration/structural information on the organic part of the As compounds (ESI MS)

Elemental specific detectionElemental specific detection Molecular specific detectionMolecular specific detection

ESAC April 2008

Page 21

concentration/structural information on the organic part of the As compounds (ESI-MS)

Courtesy Jörg Feldmann et al, Aberdeen Univ.

Separation and Identification of Organo-Arsenic SpeciesArsenic Species

100

120

167.0Peak 1 (B)[M+H]+DMAE

Peak 2

P k 1pH 5.3

60

80

%

155.1

191 1y

Peak 3

Peak 1

ICP-MS m/z 75

ICP-MS

0

20

4094.9

116.1 173.1

191.1213.1

229.0

Inte

nsity

m/z 139

m/z 167

m/z 277/ 2 9 84 10

8

132

156

180

204

228

252

276

300

m/z

100 120DMA DMAA?m/z 361

m/z 181

m/z 259ESI-MS

60

80139.0

144.1

160.1 258 9

276.980

100

120

181.0

361.0

Peak 2 (C ) Peak 3 (D)[M+H]+[M+H]+

[2M+H]+[2M+H]+0 500 1000

Retention time (s)

m/z 91

Chromatograms (above) for ICP MS

40

60

%

174.1 258.9

282.1 40

60%

144.1

Chromatograms (above) for ICP-MS measurement of As (mass 75) and ESI-MS of various indicator masses. Mass spectra (ESI-MS) for the 3 peaks show

[2M-H2O]+

0

20

72 104

136

168

200

232

264

296

328

360

203.1

0

20

72 105

138

171

204

237

270

303

336

369

163.1155.1

214.2 302.0

characteristic fragmentation patterns for the identified species – DMAE, DMA and (maybe) DMAA

ESAC April 2008

Page 22

m/z m/z

Hansen et al. J Anal At. Spectrom, 18, 474

Which Elements can be Measured Using ICP-MS?MS?

ICP-MS can also measure non-metals used in highly toxic compounds suchused in highly toxic compounds, such as pesticides and chemical warfare agents, provided the backgrounds can be controlled – e.g. using GC-ICP-MS

ESAC April 2008

Agilent GC-ICP-MS Interface

GC-ICP-MS System used:ICP-MS: Agilent 7500

Fully heated and insulated GC transfer line

Modified torch with heated injector replacesGC: Agilent 6890Interface: Agilent G3158A

Modified torch with heated injector replaces standard demountable torch

“Silicosteel” transfer line and injector liner for inertness

GC effluent injected directly into base of lplasma

Very high transport efficiency, high plasma temperature (no water vapour/aerosol) andtemperature (no water vapour/aerosol) and no solvent-based interferences

High plasma temperature means elemental g p presponse is high, even for poorly ionized elements.

Also, elemental response is independent of compound, so compound independent calibration (CIC) is possible

ESAC April 2008

( ) p

Courtesy Raimund Wahlen, LGC Teddington

I 12 00 (11 70 t 12 70) CICCAL3 DCarbon

Pesticide Analysis by GC-ICP-MS

0

2000000

4000000

6000000

8000000 Ion 12.00 (11.70 to 12.70): CICCAL3.DSingle ion chromatograms for C, P and S (right) and Cl, Br and I (below), extracted from multi-element GC-ICP-MS acquisition

3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000

200000300000400000

Ion 31.00 (30.70 to 31.70): CICCAL3.DPhosphorusLow backgrounds (due to absence of

solvent) and good ionization (due to high temperature of “dry” plasma) leads to

3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000100000

80000100000

Ion 34.00 (33.70 to 34.70): CICCAL3.DSulphur

temperature of dry plasma), leads to excellent signal to background and low LOD

Chl i

3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00020000400006000080000

3 00 4 00 5 00 6 00 7 00 8 00 9 00 10 00 11 00 12 00 13 000100000200000300000400000 Ion 35.00 (34.70 to 35.70): CICCAL3.DChlorine

Compound Conc (pg/uL - ppb) Calib Elements Elemental %3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00

200000300000400000

Ion 79.00 (78.70 to 79.70): CICCAL3.DBromine

p (pg pp )

Dichlobenil 610 Cl 41.3

2,4,6-TBA 287 Br 72.5

Ethoprop 39 P, S 12.8, 26.4

DBOB 100 Br 35 1

3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000100000

200000300000400000 Ion 127.00 (126.70 to 127.70): CICCAL3.DIodine

DBOB 100 Br 35.1

Phorate 210 P, S 11.9, 36.9

PCNB 169 Cl 60.1

Terbufos 745 P, S 10.8, 33.3

Diazinon 976 P S 10 2 10 5

3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.000100000200000 Diazinon 976 P, S 10.2, 10.5

Malathion 107 P, S 9.37, 19.4

Dursban 569 Cl, P, S 30.3, 8.82, 9.15

Ioxynil (methyl ester) 50 I 66

TPP 158 P 50 3Table (right) shows components, concentrations and l t l i ht % i 1/10 dil t d CIC ti id i

ESAC April 2008

TPP 158 P 50.3elemental weight % in 1/10 diluted CIC pesticide mix.

CIC - Sulphur in Pesticide MixSulphur elemental response is independent of the compound

Sulphur Response

Sulphur elemental response is independent of the compound

R2 = 0.9996800000

900000

TerbufosR 0.9996

600000

700000

Terbufos

Compound Concentration RT S conc S

400000

500000

Are

a

Di i

CompoundConcentration

pg/uLRT

(min)S conc (ppb)

S response

Ethoprop 385 6.4 101.64 23544

200000

300000

DursbanPhorate

Diazinon Ethoprop 385 6.4 101.64 23544Phorate 2102 7.01 775.64 261462Terbufos 7454 7.87 2280.92 785089Diazinon 9755 8.1 1024.28 360585

0

100000

0 500 1000 1500 2000 2500

EthopropMalathion

DursbanMalathion 1072 9.75 207.97 62313Dursban 5690 9.94 597.45 197738

0 500 1000 1500 2000 2500

Concentration (ppb) Pesticide compound LoD’s typically single ppb or sub-ppb

ESAC April 2008

Chemical Warfare Agent (CWA) Regulation

• Chemical Weapons Convention of January 1993

• Enforcement began April 1997

• August 24th, 2006; Meeting of 180 countries (representing 98% of World Population) which are members of the OPCW.

O i i f h P hibi i f Ch i l W• Organization for the Prohibition of Chemical Weapons

• ~70,000 Metric Tons of Chemical Weapons Declared (24/8/2006)

• ~14,000 Metric Tons Destroyed (24/8/2006)

• 2006 Budget

•$96 Million

"Determined for the sake of all mankind, to exclude completely the possibility of the use of chemical weapons..."

ESAC April 2008From Doug Richardson, Univ Cincinnati

Chemical Warfare Agent Analysis by ICP-MS

N er ve Agent s

G-Type V-Type

N er ve Agent s

G-Type V-Type

P

O

CH 3

F

O CH

CH

CH 3

CH 3

CH

P

O

CH 3

F

O CH

CH 3

CH 3P

O

CH 3 O CH 2 CH 3 P

O

CH 3 O CH 3P

O

CH 3

F

O CH

CH

CH 3

CH 3

CH

P

O

CH 3

F

O CH

CH 3

CH 3P

O

CH 3 O CH 2 CH 3 P

O

CH 3 O CH 3

F CH 3 CH 3

S oman (GD)F

S ar in (GB)S

NO

S

N

CH 3

F CH 3 CH 3

S oman (GD)F

S ar in (GB)S

NO

S

N

CH 3

VX

P

O

O

N

C NP

O

CH3

F

O

Russian VX (RVX)VX

P

O

O

N

C NP

O

CH3

F

O

Russian VX (RVX)VXTAbun (GA) Cycl osar in (GF) VXTAbun (GA) Cycl osar in (GF)

31P Selective Detection

All these agents contain a P atom, so ICP-MS can be used to identify and quantify the concentration of agent, based on the g ,consistent (compound independent) response for 31P. Nerve agents mostly decompose in the environment to MPA (via EMPA, IMPA, CMPA…)

ESAC April 2008From Doug Richardson, Univ Cincinnati

CWA Analysis in Natural Samples by LC-ICP-MS

Right: Standards

Below: Unspiked and spiked 30000

35000

31P

1

2 4 78

Apple Juice

Column: Hamilton PRP-X100 Anion Exchange

20000

25000

onse

(CP

S)

3

56 9

10g

30000 2 10000

15000

Res

po 10

20000S)

31P 13 4 7 8 9 0 5 10 15 20 25

0

5000

Elution Order1. MPA2. H2PO4

-

20000

pons

e (C

PS

Apple Juice+ Spike (3ppm)

35 6

910

0 5 10 15 20 25

Time (min)

2 43. EPA4. DMHP5. PPA6. EMPA

10000

Res

p

Apple Juice

7. IMPA8. DEHP9. IPHEP10. IBHMP0 5 10 15 20 25

0

Time (min)

ESAC April 2008

Time (min)

From Doug Richardson, Univ Cincinnati

Forensic Applications of ICP-MS –Glass Fragment AnalysisGlass Fragment Analysis

Almost any solid fragment collected from a suspect individual or location may be suitable for analysis using laser ablation ICP-MS – sample size as small as 50um diameter can be measured routinely

Glass samples can be analysed using simple screening scan (qualitative or semi-quantitative) or

lib t d i t ll h t i d fcalibrated against well-characterized reference glasses. NIST 600 series Trace Elements in Glass – eg NIST 612 ~ 50ppm

ESAC April 2008Images courtesy of New Wave Research

Trace Element Distribution Patterns (sumt 100%) S th ti Gl d U k S lto 100%) – Synthetic Glass and Unknown Samples

ESAC April 2008Data courtesy of New Wave Research

Analysis of Bic Black Pen Inks

15 black Bic pen inksdifferent sources

Non-ablated Inkdifferent sources

analyzed in triplicate

24 elements / 26 isotopes

105 comparisons taken as pairs

86/105 (82%) pairs were discriminated by Pb

Of 19 remaining, 17 pairs were discriminated by CoAblated Ink

Of 2 remaining, 1 pair was discriminated by Ba

Both Zn and Cu have similar discriminating power to Co

Only 1 pair (<1%) could not be discriminated

Most useful discriminators:Pb, Co, Ba, Cu, Zn

ESAC April 2008Images courtesy of FBI Academy

Eight Bic Black Pen Inks25.000

20.000

Unknown #2b is 02 Bic

15.000Al/Cu

Unknown #2b is 02 Bic(high W and low Mo)

10 000

Al/CuPbW/MoMo/CoZn/BaUnknown #8b is 08 Bic

10.000

(High Pb and low W)

5.000

0.00001 BicMean

02 BicMean

03 BicMean

04 BicMean

05 BicMean

06 BicMean

07 BicMean

08 BicMean

Unk (#2b) Unk (#8b)

ESAC April 2008Data courtesy of FBI Academy

Metal Imaging Mass Spectrometry ( S)(MIMS)

10 µm tissue sections

LA-ICP-MS

Slice frozen tissue, e.g. brain

D t i itiImage reconstruction Raster Laser

ESAC April 2008

Data acquisition

Images courtesy of Dominic Hare, UTS

MIMS maps of various elements in brain section of Parkinson’s disease rat model systemof Parkinson s disease rat model system

31P

Lesion side of brain(Parkinson-like)

Intact side of brain

Intensity increases from blue – green – yellow – red

EM 31P

56Fe 57Fe


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Images courtesy of Dominic Hare, UTS

Conclusions

ICP-MS offers a unique combination of:Wide elemental coverage (almost all elements can be measured)

Low limits of detection (typically 10’s ppq for easily ionized elements)Low limits of detection (typically 10 s ppq for easily ionized elements)

Wide dynamic range (from sub-ppt to 1000’s ppm)

Very rapid analysis (<3 minutes for full elemental screening, much less for consistent matrices and fewer elements)

Freedom from spectral interferences (using collision/reaction cell)

Tolerance of a wide range of matrices (due to high plasma temperature)g ( g p p )

Facility to link to chromatographic and direct solid sampling accessories, to further extend the range of applicationsg pp


Toxic and Harmful Compounds by ICP-MS final ESAC 2008.pptamcham.dk/dl/esac/ESAC08-1.pdf ·...

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Transcript of Toxic and Harmful Compounds by ICP-MS final ESAC 2008.pptamcham.dk/dl/esac/ESAC08-1.pdf ·...