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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Sz raz s ndor unicam magyarorsz g kft 1144 budapest k szeg u 29 unicam unicam hu

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]


Xseries ii icp ms

XSeriesII ICP-MS

Brief introduction to ICP-MS


Characteristics of 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

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

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 introduction1

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 introduction2

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

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

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

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

  • 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

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

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

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

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

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


Time resolved analysis

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


Xseries ii icp ms1

XSeriesII ICP-MS

Routine Environmental Applications


Environmental applications sample types

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

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

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.


Xseries ii xt interface

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


Reaching high ppm concentrations variable resolution what does it mean in practice

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 x t interface standard resolution

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 x t interface increased resolution

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 x t interface borehole water matrix

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 o es

Comparison with ICP-OES

R2 = 0.984

R2 = 0.997

n = 188


Conclusions for x series ii standard with environmental work

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.


Xseries ii icp ms2

XSeriesII ICP-MS

Performance Options

for

Environmental Research Applications


Peltier controller option do we need it

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


C ct ed when do we need it

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 enviro nmental analysis principles of collision cell technology

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 enviro nmental analysis

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

Uses for CCT - Analytes, Interferents & Gases


Spectra for upw water 35 65 amu

StandardMode

CCTMode

Spectra for UPW Water (35-65 amu)


Cct for environmental applications instrument

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

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

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 m g l

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

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

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 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 e nvironmental methods icp ms productivity pack

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

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

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


Xseries ii interference correction equations

XSeriesII - Interference Correction Equations

X Series interference correction equations derived for use with EPA protocols


Xseries ii mdls vs ilm05 3 crqls epa ilm 05 3 environmental water and waste water

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


Xseries ii environmental productivity pack

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


Xseries ii icp ms environmental analysis summary

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


Xseries ii icp ms3

XSeriesII ICP-MS

Speciation analysis


Why 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

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

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

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

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


Xseries ii icp ms for gc applications

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

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

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

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 xseries ii icp ms

The New XSeriesII ICP-MS

More Practicality, More Productivity, More Performance for every application


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