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Száraz Sándor Unicam Magyarország Kft. 1144 Budapest, Kőszeg u. 29. unicam@unicam.hu

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

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Száraz Sándor Unicam Magyarország Kft. 1144 Budapest, Kőszeg u. 29. unicam@unicam.hu

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  1. A Thermo Electron Corporation új XSeriesII ICP-MS készülékének és környezetvédelmi alkalmazásainak bemutatása Száraz Sándor Unicam Magyarország Kft. 1144 Budapest, Kőszeg u. 29. unicam@unicam.hu

  2. XSeriesII ICP-MS Brief introduction to ICP-MS

  3. Characteristics of ICP-MS • Wide element coverage • Low limits of detection • Elemental and isotopic information • Wide dynamic range • Wide variety of samples

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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

  9. 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)

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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)

  15. 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

  16. 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

  17. 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

  18. XSeriesII ICP-MS Routine Environmental Applications

  19. 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)

  20. 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

  21. 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.

  22. 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

  23. 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

  24. 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

  25. 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

  26. Long Term Drift of X Series with Xt Interface (Borehole Water Matrix) Li = 21 µg l-1 RSD = 1.6 % In = 10 µg l-1 RSD = 1.1 % U = 4 µg l-1 RSD = 1.5 %

  27. Comparison with ICP-OES R2 = 0.984 R2 = 0.997 n = 188

  28. 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.

  29. XSeriesII ICP-MS Performance Options for Environmental Research Applications

  30. 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

  31. 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

  32. Introduction to the use of CCT with environmental analysis:Principles of Collision Cell Technology Iron Argon Oxygen Helium

  33. 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?

  34. Uses for CCT - Analytes, Interferents & Gases

  35. StandardMode CCTMode Spectra for UPW Water (35-65 amu)

  36. 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”

  37. CCT for environmental applications: Experimental - considerations Wide range of typical environmental analytes were measured: - 30 analytes, 55 isotopes Many analytes have associated interference problems….

  38. 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

  39. CCT for environmental applications:Results - detection limits (mg/L) Based on 3s on 12x10replicates of blank, each from a new calibration

  40. CCT for environmental applications:Results – stability of real sample in different modes Sample diluted 1+9 and spiked to 2% HCl

  41. 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

  42. 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)

  43. 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

  44. 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

  45. 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

  46. XSeriesII - Interference Correction Equations X Series interference correction equations derived for use with EPA protocols

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

  48. 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

  49. 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

  50. XSeriesII ICP-MS Speciation analysis

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