A Thermo Electron Corporation új XSeriesII ICP-MS készülékének és

környezetvédelmi alkalmazásainak bemutatása

Száraz SándorUnicam Magyarország Kft.1144 Budapest, Kőszeg u. 29.

unicam@unicam.hu

XSeriesII ICP-MS

Brief introduction to ICP-MS

Characteristics of ICP-MS

• Wide element coverage• Low limits of detection• Elemental and isotopic

information

• Wide dynamic range• Wide variety of samples

ICP-MS Process

• 4 Basic Stages1. Sample Introduction and Ion

Generation2. Ion Focusing

3. Separation of Analyte Ions in Quadrupole Mass Filter

4. Ion Detection

Ar PlasmaCellQuadDetector

SampleGas

1.

M+ Species Generated

in the Plasma

2.

Ion Focusing / Optional

Collision Cell

M+M+

4.

Ion Detection by electron multiplier

3.

Ion Analysis Separation by

m/z ratio

M+

ICP-MS - Sample Introduction

As the solution passes throughthe Ar plasma, 4 main processeswill occur

• Samples are normally analyzed as solutions

• Sample is introduced into an argon plasma as a fine aerosol, via a peristaltic pump, nebulizer and spray chamber

• Within the plasma (< 6000K) the solvent is evaporated and the sample species are decomposed into their constituent atoms and ionised

- Ionisation process is extremely efficient in the plasma, and contributes to the high sensitivity of ICP-MS

ICP-MS - Sample Introduction

• Normally via concentric nebulizer ~1ml/min uptake

• Typical sample volume - 20 elements using 3 x 2 secs. integrations - 4 - 5ml sample required

• Optional low flow nebulizer for μl. sample analysis

• Optional laser ablation for direct solids analysis

ICP-MS - Sample Introduction

• Maximize M+- Minimize MO+- Minimize M++

• Sample Uptake- Nebulizer dependent

• Plasma Gases- Cool- Auxiliary- Nebulizer dependent

• Torch Position- x, y, z control

Hotter

M++M+MO+

Cooler

Ion Sampling and Focusing

• Ions formed in the plasma are extracted through a sample and skimmer cone arrangement

• Ion Lenses focus & optimize ion transmission to quadrupole analyser

• Sample treatment is important to minimize deposition on cones:-

- Dissolve and dilute to ~ 0.2% w/v- up to ~ 5% nitric acid preferred - up to ~ 5% hydrochloric acid- ~ 1% hydrofluoric acid (using an

Inert Sample Introduction Kit), phosphoric acid or sulfuric acid Increasing vacuum

Sample Cone

Skimmer ConeIon

LensDA

Extraction Lens

Slide Valve

Ion Focusing Mechanism

• Optimizes ion transmission to quadrupole analyser

• Conventional ion focusing devices - Complex lens configuration and often

incorporate a photon stop- Backgrounds typically 10-20 cps

• XSeriesII: New high efficiency ion guide- Simple design with reduced number

of lenses- Incorporate an innovative chicane deflector

and off-axis quadrupole- Backgrounds of <0.5 cps- Upgradeable to collision cell technology

(CCT)

Ion Analysis – Quadrupole MS

• Quadrupole consists of 4 rods mounted equidistant to each other around the circumference of a circle

• Separates Ions according to their mass to charge (m/z) ratio

• Principles of operation- Alternating RF / DC potentials are applied to the quadrupole rod pairs

- Ions move in a spiral motion down the quadrupole axis

- Majority of masses are put into an unstable trajectory and are rejected

- However under a given condition, ions of a specific m/z will pass through the analyser and reach the detector

Ion Detection

• Ion detection is made with an electron multiplier

• Measures the number of Ions arriving at the detector - proportional to the concentration of that isotope in the original solution

• Detector operates in pulse counting (ion counting) and analogue (ion current) modes

• With automatic cross calibration measures major, minor and trace analytes in a single acquisition

-2Kv-2Kv

Data Acquisition Modes

• Scanning- Qualitative analysis and Quantitative analysis- SemiQuantitative analysis: Post run data retrieval on un-

calibrated elements

• Peak Jumping- Selected isotopes- Optimized dwell times- Improved detection limits

• Time Resolved Analysis- Transient signal analysis- Applicable to laser ablation ICP-MS and chromatographic

studies

ICP-MS Full Mass Spectrum

• Simple spectra (primary M+ ions)- Facilitates simple interpretation

• Very high signal to background- Low detection limit capabilities

V ICP-AES Spectra - Vanadium 10mg/LV ICP-MS Spectra - Vanadium 10mg/L

Calibration Techniques

• Semi Quantitative- Analyte sensitivity can be determined from the instrument

response built from the response to other known analytes.- Relative Sensitivity Factors (RSF) apply corrections for

ionization and sample processing effects, these can be pre-determined for a given matrix to improve accuracy

• Full Quantitative- Multi element external calibration standards- Standard additions calibration- Isotope ratio determination (for isotope dilution measurement)

Semi-Quantitative Analysis

• External standards not required for each analyte

• Calibration via RSFs from Response Curve

Semi Quantitative Calibration Plot

• Full elemental and isotopic information

• Major to trace concentration determined

• No prior knowledge of sample required

Fully Quantitative Analysis

• External calibration standards measured prior to unknown samples

• Element or isotope responses are plotted against concentration

• Concentration of unknown samples calculated from the calibration graph

External Calibration

• Known sample is spiked with known concentrations of analytes

• Standard addition calibration plot provides accurate low level concentration data from the x-axis intercept

• Eliminates need for matrix matched calibration standards

Standard Additions

3.8 6.0 8.1 10.3Time (min)

AsC +AsB

As(III)

DMA

MMA

As(V)

Time Resolved Analysis

• Enables time resolved data to be acquired both qualitatively and quantitatively from transient signals

• Wide applicability including Laser Ablation ICP-MS and chromatographic studies

XSeriesII ICP-MS

Routine Environmental Applications

Environmental Applications – Sample types

• Wide variety of environmental sample types

Drinking water Ground water Waste water / effluent Leachates Soil / contaminated land digests Sediment digests Plant / animal tissue digests

• Generally high sample numbers (>100 per day in many laboratories)

Enviromental applications:Myths and misconceptions in ICP-MS

• Considered in the flame AA, furnace AA and ICP-OES communities that:

Not possible to measure high ppm concentrations (>100ppm) by ICP-MS

Interferences are a significant problem

Instrumentation is complex and difficult to use

Very high cost

Memory effects vs wide dynamic range: Monitored Sample Uptake and Wash

•Intelligent sample monitoring to ensure stability prior to data acquisition.

•Monitored washout eliminates sample carry over.

XSeriesII - Xt Interface

• Optimized response for Environmental Analysis

• Maximum productivity through long-term matrix tolerance and excellent signal stability

• Minimum recalibrations between samples

• Extended dynamic range- Enables Linear determination of

Na,Mg,K,Ca to 200 mg/L- >> 1000mg/L when used in

conjunction with high resolution measurement

Reaching high ppm concentrations:Variable resolution – what does it mean in practice?

• Allows the user to extend the dynamic range even further

The dynamic range limitation then becomes the 0.2% total dissolved solids upper level imposed by the interface cones

• Can be adjusted down to peak widths lower than 0.3 amu

• Can be adjusted on-the-fly to allow standard and ‘high’ resolution measurements to be made analyte by analyte

RF

DC

MM+1

M-1

Na, Ca, calibration – Xt interface, standard resolution

Na: blank to 300 ppm

Standard XSeriesII configuration (no CCT), using In as the internal standard

Sensitivity = 0.9 Mcps/ppmBEC = 107 ppb

Cr: blank to 100 ppb

Sensitivity = 1.3 Mcps/ppmBEC = 0.2 ppb

Peak width (at 10% peak height) = 0.75 amu

Reaching even higher ppm concentrations:Na calibration – Xt interface, increased resolution

Na: blank to 2000 ppm

Standard XSeriesII configuration (no CCT), using Ga as the internal standard

Sensitivity = 0.5 Mcps/ppmBEC = 38 ppb

Peak width (at 10% peak height) = 0.2 amu

2000 ppm

Long Term Drift of X Series with Xt Interface (Borehole Water Matrix)

0.90

0.95

1.00

1.05

1.10

0 2 4 6 8 10 12 14 16 18

Time /hours

Rela

tive

resp

onse

7Li 115In 238U

Li = 21 µg l-1 RSD = 1.6 %

In = 10 µg l-1 RSD = 1.1 %

U = 4 µg l-1 RSD = 1.5 %

Comparison with ICP-OES

Calcium

0

50

100

150

200

250

300

0 50 100 150 200 250 300

ICP-MS mg l-1

ICP-

AES

mg

l-1

Potassium

0

20

40

60

80

100

0 20 40 60 80 100ICP-MS mg l-1

ICP-

AES

mg

l-1

R2 = 0.984 R2 = 0.997

n = 188

Conclusions for XSeriesII standard with environmental work

•Hardware and software advancements of the XSeriesII ICP-MS allow rapid, accurate analyses of environmental samples with turnkey operation.

•Great improvement in sample throughput.

•Linear range extended and matrix tolerance improved with Xt interface.

•Protocol compliance even without CCT.

XSeriesII ICP-MS

Performance Options for

Environmental Research Applications

Peltier Controller option – do we need it?• Rapid, precise temperature control

of spray chamber for optimum performance- constant aerosol formation independent of the laboratory temperature control

• Typical operation at 2oC- reduced solvent loading into the plasma - lower oxides and other interferences- improved MDLs

• Can be used with the standard quartz or inert spray chamber

• Rapid changeover between aqueous and organic matrices using the organics kit

Variable temperature Peltier (thermo-electric) block

CCTED – When do we need it?

• Research Applications• Ultimate Detection Limits - well

below regulatory levels• Analysis of some complex or

pristine environmental matrices such as seawater or snow / ice.

- Common interferences can not be eliminated using conventional quadrupole ICP-MS technology

- Interference correction equations- Matrix removal

• CCTED enables direct analysis without the need for matrix removal leading to improved DLs and enhanced productivity

Element m/z InterfencesK 39 ArHCa 40 ArV 51 ClO, ArCCr 52 ArC, ClOHMn 55 ClOFe 56 ArO, CaOCo 59 ArNa, CaOHCu 63 ArNaZn 66 ArMgAs 75 ArClSe 80 ArAr

Introduction to the use of CCT with environmental analysis:Principles of Collision Cell Technology

Isotope Interferant Isotope Interferant 6,7Li Background 52Cr ArC, ClOH 23Na Background 55Mn ClO, KO 28Si N2, CO 56Fe ArO, CaO 31P NOH 59Co ArNa, CaOH 32S O2 63Cu ArNa

39,40K ArH, Ar 66Zn ArMg 40Ca Ar 75As ArCl, CaO2 48Ti SO 80Se Ar2, FeH2O 51V ClO, ArC 81Br Ar2H

IronArgonOxygen

Helium

Introduction to the use of CCT with environmental analysis

• Some analytes have few interference problems and perform best with the cell unpressurised, i.e. standard ICP-MS mode, e.g. Pb

• The ideal multi-element analysis would result in several analyses under different conditions, e.g.

Standard mode H2 mode NH3 mode

• A more efficient method is to switch modes “in-sample”

is this viable in terms of speed, stability and accuracy?

Uses for CCT - Analytes, Interferents & Gases

Mass / amu Analyte Interferent Gas24 Mg CC H2 / He28 Si N2 H2 / He32 S O2 Xe / He1

39 K ArH H2 or NH3 / He40 Ca Ar H2 or NH3 / He51 V ClO NH3 / He52 Cr ArC H2 / He54 Fe ArN H2 / He56 Fe ArO H2 or NH3 / He63 Cu ArNa H2 / He66 Zn ArMg H2 / He72 Ge ArAr H2 / He75 As ArCl H2 / He77 Se ArCl H2 / He78 Se ArAr H2 / He80 Se ArAr H2 / He82 Se ArHArH H2 / He

Spectra for UPW Water (35-65 amu)

CCTCCT ModeMode

StandardStandard ModeMode

CCT for environmental applications: Instrument

• XSeriesII ICP-MS with CCTED and Xt interface

• CCT connected to two gases:

8% H2 in He 1% NH3 in He

• 2 computer controlled MFCs allow gases to be changed “in-sample”

Wide range of typical environmental analytes were measured: - 30 analytes, 55 isotopes

Many analytes have associated interference problems….

CCT for environmental applications: Experimental - considerations

Mass / amu Analyte Interferent Gas24 Mg CC H2 / He28 Si N2 H2 / He32 S O2 Xe / He1

39 K ArH H2 or NH3 / He40 Ca Ar H2 or NH3 / He51 V ClO NH3 / He52 Cr ArC H2 / He54 Fe ArN H2 / He56 Fe ArO H2 or NH3 / He63 Cu ArNa H2 / He66 Zn ArMg H2 / He72 Ge ArAr H2 / He75 As ArCl H2 / He77 Se ArCl H2 / He78 Se ArAr H2 / He80 Se ArAr H2 / He82 Se ArHArH H2 / He

Uptake

25s

CCT for environmental applications:Experimental - Timing

Anal

ytes

SettleDelay

30s

Settle Delay

30s

StandardMode

3x18s reps

Wash

25s

Total Time Per Sample (3 repeats) = 3 minutes, 45 seconds

Tim

e Pr

ofile

VCr

NH3/He

3x1.6s reps

LiBeNaRbSrRbMoAgCdSnCsBaTlPbU

MgAlK

CaCrFeMnNiCuZnGaAsSe

H2/He

3x18s reps

7Li 0.01 55Mn 0.01 77Se 0.1 114Cd 0.0039Be 0.003 56Fe 0.06 78Se 0.03 118Sn 0.0123Na 2 58Ni 0.02 80Se 0.03 120Sn 0.00924Mg 0.1 59Co 0.005 82Se 0.1 133Cs <0.00125Mg 0.3 60Ni 0.03 85Rb 0.004 138Ba 0.00727Al 0.2 63Cu 0.02 87Rb 0.008 140Ce <0.00140Ca 3 64Zn 0.05 88Sr 0.005 203Tl 0.00244Ca 1 65Cu 0.02 95Mo 0.007 205Tl 0.00151V 0.01 66Zn 0.05 98Mo 0.005 206Pb 0.0152Cr 0.2 69Ga 0.02 107Ag 0.009 207Pb 0.0153Cr 0.05 71Ga 0.005 109Ag 0.009 208Pb 0.00954Fe 1 75As 0.01 111Cd 0.002 238U <0.001

H2/He ModeNH3/He ModeStandard Mode

CCT for environmental applications: Results - detection limits (g/L)

Based on 3 on 12x10 replicates of blank, each from a new calibration

Stability of NIST 1640x10 - 10 Hours, 12 Different Calibrations

0

0.5

1

1.5

2

2.5

0 2 4 6 8 10

Time (Hours)

Conc

entra

tion

(ug/

L)

51V NH3 Mode (1.5%)

80Se H2 Mode (1.7%)

111Cd Std Mode (0.3%)

CCT for environmental applications: Results – stability of real sample in different modes

Sample diluted 1+9 and spiked to

2% HCl

CCT for environmental applications:Conclusions

• The XSeriesII allows rapid settings changes, allowing two different cell gases and normal ICP-MS mode to be used in a single sample analysis

3¾ minutes per sample, 55 isotopes, 3 measurements/isotope,

• Excellent stability is retained in each mode RSDs of typically <1% over a 12 hour duration for a signal of

~50,000cps

• Mode switching allows the optimum conditions for each analyte to be utilised, resulting in ultimate performance:

DLs in the ppt or sub-ppt range for almost all elements

• The technique results in freedom from many interferences

Accuracy of within ±5% for the vast majority of analytes, even after spiking to 700ppm chloride

Xs Interface option – do we need it?• Xs- extraction provides enhanced

sensitivity whilst retaining the extremely low background characteristics of the XSeriesII

• For research and ultra trace applications

- Actinides - Isotope ratios- Small spot laser applications

• Interchangeable with the Xi interface- User interchangeable ~ 2 minutes

• Typical sensitivity >200Mcps/ppm for mid –high mass elements (In – U)

X Series Environmental Methods ICP-MS Productivity Pack

• Supplied to customers on instrument delivery: PlasmaLab Productivity Method Template

Detailed instructions on instrument set-up, solution preparation and sample analysis

A Productivity Method Template that can be modified to a laboratory’s own working method

All calibration and quality control solutions required to run each protocol

A printed file containing the Productivity Method Template

Environmental Protocols

• US EPA has developed a series of methods for the analysis of drinking water, waste water and other environmental samples: -

OW 200.8 drinking water 1991

OSW 6020 waters, wastes, soils, etc 1994

OSW 6020A waters, wastes, soils, etc 1998

CLP ILM05.2D waters, wastes, soils, etc 2001

These are challenging, QC intensive, multiple analyte, multiple concentration methods with tough specifications for accuracy, precision and DLs

Environmental Protocols - Typical Requirements

• Methods are ‘Prescriptive’ with specific rules on various analytical practices that must be followed e.g.

• Specified Elements: Up to 23 elements, 7-orders of magnitude range (ppt to high ppm)

• QC Checks – post calibration: Separate source calibration verification Interference check - High Matrix Interference check - High Matrix + Spike

• QC Checks – every 10 samples: Continuing calibration verification Reference material Detection limit check standard

• Sample QCs - every 20 samples: Duplicate Serial Dilution and Spike Recovery

XSeriesII - Interference Correction Equations

X Series interference correction equations derived for use with EPA protocols

XSeriesII MDLs vs. ILM05.3 CRQLs- EPA ILM 05.3 Environmental water and waste water

0.001

0.01

0.1

1

10

100

1000

10000

Con

cent

ratio

n ug

/L (p

pb)

Analyte

9Be

23Na

25Mg

27Al

39K44C

a51V52C

r55M

n56Fe59C

o60N

i65C

u66Zn75A

s77S

e78S

e82S

e107A

g114C121S

b137B

a205Tl208P

b

Comparison of XSeriesII MDLs and CLP CRQLs

XSeriesII MDL0.5*CRQL

0.001

0.01

0.1

1

10

100

1000

10000

Con

cent

ratio

n ug

/L (p

pb)

Analyte

9Be

23Na

25Mg

27Al

39K44C

a51V52C

r55M

n56Fe59C

o60N

i65C

u66Zn75A

s77S

e78S

e82S

e107A

g114C121S

b137B

a205Tl208P

b

Comparison of XSeriesII MDLs and CLP CRQLs

9Be

23Na

25Mg

27Al

39K44C

a51V52C

r55M

n56Fe59C

o60N

i65C

u66Zn75A

s77S

e78S

e82S

e107A

g114C121S

b137B

a205Tl208P

b

Comparison of XSeriesII MDLs and CLP CRQLs

XSeriesII MDL0.5*CRQL

PlasmaLab Productivity Method Template on CD

Detailed instructions on instrument set-up, solution preparation and sample analysis

Productivity Method Template can be modified to a laboratory’s own SOP

All calibration and quality control solutions required to run each protocol

A printed file containing full instructions of the operating procedure

XSeriesII Environmental Productivity Pack

Environmental Productivity Pack - Contents

Supplied to customers on instrument delivery:

XSeriesII ICP-MS – Environmental Analysis Summary

• Routine MDLs - XSeriesII ICP-MS easily provides protocol compliant

detection limits QC checks: XSeriesII consistently produces accurate results on

QCs and samples Interference checks : XSeriesII design offers excellent freedom

from interference and stable correction where necessary Fastest sample throughput with protocol compliance

• Productivity Pack uniquely offers: Proven, reliable off-the-shelf EPA methods for the - XSeriesII ICP-

MS Unbeatable rapidity of start-up after installation

• Research Peltier cooled spray chamber for improved long term stability and

MDLs CCTED for interference removal / improved accuracy and detection

limits in complex matrices Xs interface for special applications requiring the ultimate

signal/background LC / GC packages for speciation studies

XSeriesII ICP-MS

Speciation analysis

Why Speciation Analysis?• Elemental speciation data

can reveal valuable information in addition to total element concentrations: -

bioavailability, mobility, metabolic processes, bio transformations and toxicity implications

• Elemental speciation is receiving increasing interest in both academic & commercial laboratory environments

Applications often use HPLC-ICP-MS and GC-ICP-MS techniques

Growing number of publications for elemental speciation analyses

Elemental speciation increasingly recognised in EPA protocols

Inorganic As3+ arsenite (AsO3)3-

Inorganic As5+ arsenate (AsO4)3-

Monomethylarsonate (MMA)

Dimethylarsinate (DMA)

Arsenobetaine ((CH3)3As+CH2COOH)-

Arsenocholine ((CH3)3As+

(CH2)2OH)

Increasing Increasing ToxicityToxicity

e.g. Arsenic Toxicity

Topical Species in Environmental, Life Science and Food Samples

• Arsenic – (As5+, As3+, DMA, MMA, AB) urine, biological tissues, foods, waters

• Chromium – (CrVI and CrIII) biological fluids, waters

• Selenium – (SeIV, SeVI, SeMet, SeEth, SeMC) urine, biological tissues, foods & supplements,

• Mercury – (Hg2+, MeHg) biological tissues, foods, waters

• Tin – (MBT, DBT, TBT) biological tissues, foods, waters

Flexible HPLC-ICP-MS product packages

• XSeriesII ICP-MS with Finnigan Surveyor HPLC

• XSeriesII ICP-MS with SpectraSYSTEM HPLC

• ‘HPLC Coupling Packs’ for X Series ICP-MS

Simple analytical and electrical connections to ‘any’ HPLC

External Trigger Board for 2-way communications between the LC and the ICP-MS

X Series ICP-MS for HPLC applications

• Simple to interchange between standard ICP-MS & HPLC sample introduction

• XSeriesII ICP-MS organics kit for reverse/normal phase HPLC

• Burgener AriMist nebulizer for mobile phases with high TDS & 50–2000 μL/min flow rates

• Sensitive multi-element capability

• Field upgradeable XSeriesII ICP-MS

Flexible GC-ICP-MS product packages

• XSeriesII ICP-MS with Finnigan Focus GC

• XSeriesII ICP-MS with Finnigan Trace GC

• ‘GC Coupling Packs’ for XSeriesII ICP-MS

Simple analytical and electrical connection to ‘any’ GC

XSeriesII ICP-MS for GC applications

• Unique DUAL MODE sample introduction Gas or solution analyses

without reconfiguring the interface

Three legged GC-ICP-MS torch

Flexible tuning & performance testing with aqueous solution

On-line addition of aqueous internal standards

Robust plasma conditions for GC-ICP-MS analysis

Speciation with LC-ICP-MS: Arseno sugars in kelp

• SpectraSYSTEM HPLC mobile phase: 5 mM TBAH at pH 6.0 (0.7 ml/min) HPLC column: Discovery C18 (150mm x 2.1mm i.d) 0.2 g kelp extracted in 5ml MeOH/water (50:50 v/v) Injection volume: 1 micro-litre Dimethylarsinoylriboside standards (deionised water) Fast separation, baseline separation

of all peaks in just over 2 mins.

• LC-ICP-MS Coupling Pack• XSeriesII ICP-MS

Xt interface PlasmaScreen Plus Peltier Cooled Spray Chamber

Arsenosugar II

Arsenosugar III

Arsenosugar I

Arsenosugar IV

Speciation with GC-ICP-MS Organo-Sn speciation in Sediments

• Finnigan Focus GC GC column: 30 m Restek MXT-1 Mobile phase: He at 25 ml/min Make-up gas: Ar 350 ml/min Injection volume: 1 μL Oven program: 70-250ºC (50ºC/min plus 1 minute hold)

• GC-ICP-MS Coupling Kit

• XSeriesII ICP-MS Xt interface PlasmaScreen Plus Timeslice internal standard: (5 ng/ml Sb)

PlasmaLab for chromatographic applications

• Transient TRA data acquisition

• External Triggers for controlling ‘any’ HPLC or GC accessory

• Intelligent bi-directional communication for failsafe, high throughput analysis

• Unique ‘Timeslice’ & ‘Transient’ internal standard modes for improved data quality

• In-house peak integration for quantitative analysis

The New XSeriesII ICP-MSMore Practicality, More Productivity, More Performance for every application