A Thermo Electron Corporation új XSeries
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A Thermo Electron Corporation új XSeries II ICP-MS készülékének és környezetvédelmi alkalmazásainak bemutatása. Száraz Sándor Unicam Magyarország Kft. 1144 Budapest, Kőszeg u. 29. [email protected] XSeries II ICP-MS. Brief introduction to ICP-MS. Characteristics of ICP-MS.

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A Thermo Electron Corporation új XSeriesII ICP-MS készülékének és környezetvédelmi alkalmazásainak bemutatása

Száraz Sándor

Unicam Magyarország Kft.

1144 Budapest, Kőszeg u. 29.

[email protected]


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


3.

Ion Analysis Separation by m/z ratio

2.

Ion Focusing / Optional Collision Cell

1.

M+ Species Generated in the Plasma

4.

Ion Detection by electron multiplier

M+

M+

M+

Detector

Quad

Cell

Ar Plasma

Sample

Gas

ICP-MS Process

  • 4 Basic Stages

    1. Sample Introduction and Ion Generation

    2. Ion Focusing

3. Separation of Analyte Ions in Quadrupole Mass Filter

4. Ion Detection


ICP-MS - Sample Introduction

  • 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

As the solution passes through

the Ar plasma, 4 main processes

will occur


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


MO+

M+

M++

Cooler

Hotter

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


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 quadrupoleanalyser

  • 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

Slide Valve

Skimmer Cone

Ion Lens

Sample Cone

DA

Extraction Lens

Increasing vacuum


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-MS Spectra - Vanadium 10mg/L

V ICP-AES 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

  • Full elemental and isotopic information

  • Major to trace concentration determined

  • No prior knowledge of sample required

Semi Quantitative Calibration Plot


Fully Quantitative Analysis

External Calibration

  • 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

Standard Additions

  • 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


As(III)

DMA

AsC +

AsB

As(V)

MMA

8.1

6.0

10.3

3.8

Time (min)

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 dynamicrange

    • EnablesLinear determination of Na,Mg,K,Ca to 200 mg/L

    • >> 1000mg/L when used in conjunction with high resolution measurement


DC

M-1

M

M+1

RF

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


Na, Ca, calibration – Xt interface, standard resolution

Na: blank to 300 ppm

Cr: blank to 100 ppb

Sensitivity = 0.9 Mcps/ppm

BEC = 107 ppb

Sensitivity = 1.3 Mcps/ppm

BEC = 0.2 ppb

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

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

2000 ppm

Sensitivity = 0.5 Mcps/ppm

BEC = 38 ppb

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

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


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

Li = 21 µg l-1RSD = 1.6 %

In = 10 µg l-1RSD = 1.1 %

U = 4 µg l-1RSD = 1.5 %


Comparison with ICP-OES

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


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

Iron

Argon

Oxygen

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


StandardMode

CCTMode

Spectra for UPW Water (35-65 amu)


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”


CCT for environmental applications: Experimental - considerations

Wide range of typical environmental analytes were measured:

- 30 analytes, 55 isotopes

Many analytes have associated interference problems….


CCT for environmental applications:Experimental - Timing

Li

Be

Na

Rb

Sr

Rb

Mo

Ag

Cd

Sn

Cs

Ba

Tl

Pb

U

Mg

Al

K

Ca

Cr

Fe

Mn

Ni

Cu

Zn

Ga

As

Se

V

Cr

Analytes

Uptake

25s

NH3/He

3x1.6s reps

Settle

Delay

30s

H2/He

3x18s reps

Settle

Delay

30s

Standard

Mode

3x18s reps

Wash

25s

Time Profile

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


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

Based on 3s on 12x10replicates of blank, each from a new calibration


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 water1991

    • OSW 6020 waters, wastes, soils, etc1994

    • OSW 6020Awaters, wastes, soils, etc 1998

    • CLP ILM05.2Dwaters, wastes, soils, etc2001

      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

  • QCChecks – 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


XSeriesII Environmental Productivity Pack

Supplied to customers on instrument delivery:

  • 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

Environmental Productivity Pack - Contents


XSeriesIIICP-MS – Environmental Analysis Summary

  • Routine

    • MDLs - XSeriesIIICP-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?

e.g. Arsenic Toxicity

  • 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 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


Arsenosugar II

Arsenosugar IV

Arsenosugar III

Arsenosugar I

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 separationof all peaks in just over 2 mins.

  • LC-ICP-MS Coupling Pack

  • XSeriesII ICP-MS

    • Xt interface

    • PlasmaScreen Plus

    • Peltier Cooled Spray Chamber


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-MS

More Practicality, More Productivity, More Performance for every application


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