3 Comparison of ICP-MS to Other Techniques Shares applications with ICP-AES and AAShares multielement characteristic with ICP-AESShares analytical speed with ICP-AESShares detection limits with GFAASUnique in isotope measurement capabilityUnique in rapid semiquantitative analysis
4 X Series ICP-MS Training Course Introduction to ICP-MS theory and X Series ICP-MSPlasmaLabAnalytical Method DevelopmentDealing with interferences
6 Introduction to ICP-MS Theory and X Series ICP-MS LiKRbCsFrBeMgCaSrBaNaScYLaAcTiZrHfVNbTaRaCrMoWMnTcReFeRuOsCoRhIrNiPdPtCuAgAuZnCdHgGaInTlGeSnPbAsSbBiTePoBrIAtKrXeRnSeBAlCSiNPSFClNeArOCeThPrPaNdUPmNpSmPuEuAmGdCmTbBkDyCfHoEsErFmTmMdYbNoLuLrHeSamples takemany formsthroughout ourenvironmentThe varying sample types place high demands uponthe instrument design
8 SPETTROSCOPIA ATOMICA ICP-MSICP-OESGF-AASFlame AA100%0.1 %ppmppbpptppqRange di misure
9 ICP-MS : Inductively Coupled Plasma - Mass Spectrometry ICP-MS INTRODUZIONEICP-MS : Inductively Coupled Plasma - Mass SpectrometryTecnica multielementaleAmpio range di elementi analizzabili (> 75)Detection Limits di ng/L in soluzioneAlta produttività (campioni /giorno : 500)Range dinamico di linearità esteso
10 ICP-MS ASPETTI FONDAMENTALI ICP : Sorgente di ioni Atomi e Molecole IoniMass Spectrometer : FiltroGli ioni vengono separati in funzione del rapporto m/zSegnale proporzionale al numero di ioni
11 X SeriesII ICP-MS Il Più piccolo ICP-MS da banco La più alta produttività analitica tramite le conformità ai protocolli analiticiConfigurazioni dedicateSpettrometro praticamente esente da manutenzioneSoftware consolidato PlasmaLab™ Windows®Espandibilità Plug-and-Play
12 Il più piccolo ICP-MS da banco ICP-MS Sviluppato per far fronte alle scarse possibilità di spazio dei moderni laboratoriDimensione110x54cm – Installabile su banchi di laboratori standardCompatibilità con “Clean room”Ridotti valori di dissipazione termica e portata di aspirazione- Minori costi di installazione e di funzionamentoSmallest bench top ICP-MSDesigned with today’s busy laboratories in mind, where space is often at a premium - E.g. small contract labs110x54cm “footprint”- Comparable to many competitive AA systemsInstallable onto a standard laboratory bench – the LHS of the instrument can be fitted right up to the wall. Access is required from the front and RHS only for servicing.Clean room compatible – polymer metal free casingHeat dissipation and extraction requirements are minimized, reducing set-up and running costs – rotary pump & chiller can be sited remotely reducing setup and air conditioning costs.
13 Characteristics of conventional ICP-MS DetectionWe can divide the ICP-MS process into 4 stagesFiltrationOptimizationThe technique isunique in that the sampleis brought into the systemunder atmospheric pressurebut the system itself operatesunder high vacuum.Sample Introduction
14 SISTEMA DI INTRODUZIONE DEL CAMPIONE Introduzione campione liquidoNebulizzatori & SpraychambersSistemi di desolvatazioneHPLCFlow InjectionIntroduzione campione solidoETVLaser AblationIntroduzione campione gassosoGeneratore di vaporiGas cromatografo
16 Sample Introduction – Aerosol formation The fundamental purpose of the nebulizer isFormation of Aerosoland the fundamental purpose of the spray chamber isAerosol Filtering
17 Droplet size No. of Droplets too large Droplet size ~10micron Only this region should pass to the plasmaH.Willard, LMerritt, J.Dean, F.Settle:Instrumental Methods of Analysis; Wadsworth Publishing Company
18 Controllo di temperatura ad effetto Peltier Blocco a temperatura variabile Peltier (thermoelettrico)Controllo rapido e preciso della temperatura della camera di nebulizzazionePassaggio rapido da matrici acquose ad organiche, con l’impiego del Kit organiciPeltier ControllerFitted to the X7 as standard the Peltier block is electronically controlled enabling the spray chamber to be cooled and operated at a precise temperature.This can lead to reduced molecular species due to lower solvent loading in the plasma and improved Method LOD’s due to improved long term stability.Temperature stabilization between aqueous and organic analysis is reduced to ~ minutes compared to >2hours with competitive systems that use water-cooled spray chambers.
19 Sistema intelligente di introduzione campione PICO Monitor – sistema di monitoraggio intelligente di aspirazione campione e lavaggioAggiunta di standard interni in conformità ai protocolliCompatibile con nebulizzatori a basso flusso e convenzionaliControllo totale di autocampionatore e pompa peristaltica –Tramite ACL scriptsIntelligent Sample IntroductionPICO Monitor – Intelligent monitored uptake and rinseMonitors the Internal Standard during sample uptake and user defined elements (e.g. matrix elements) during washout – enables the A/S to move to the next sample in the shortest possible time WITHOUT incurring sample carry overProtocol compliant addition of the internal standard(s)Can be added on-line simply by a tee-piece or PrepLabConventional & low flow nebulizers compatibleFor clinical samples and semi-con. wafer-wash samplesFull autosampler and peristaltic pump controlACL scripts for enhanced productivityAccessory Control Language scripts enable the A/S and peri-pump to be programmed by the user - for example the peri-pump is computer controlled and can be speeded up between samples to improve sample washout and the A/S probe can be returned to the wash station prior to the termination of data acquisition.By using solution still in the uptake tubing to complete the data acquisition sample throughput can be considerably increased.An independent evaluation by a PQXL user has shown a reduction in sample-to-sample analysis time from 7 minutes to 2.5 minutes with the X Series using real high matrix environmental samples without any degradation in precision or MDLs. See Application Note S371AN
20 Sample Introduction – Ionisation The filtered aerosol (still at atmospheric pressure)then passes to the Plasma where the primary process is theFormation of IONSCool GasAux GasLoad CoilNeb GasTorch
29 Plasma Formation Intense analyte emission Current Magnetic fieldFlow of ions and electronsIntense analyte emissionConcentric quartz tubesSample aerosol and argonMagnetic fieldsArgon coolant flowH.Willard, LMerritt, J.Dean, F.Settle:Instrumental Methods of Analysis; Wadsworth Publishing Company
35 LA SORGENTE AL PLASMA Formazione degli ioni Il campione passa attraverso il plasma e cambia da aerosol a vapore poi viene atomizzato e ionizzato
36 LA SORGENTE AL PLASMA Formazione degli ioni MO + M M+ MX (MX) n RecombinazioneMO +M(H2O) +X-Campione(viscosità, tensione superficiale,...)Distribuzione dellegocce di aerosolDesolvatazioneVaporizzazioneDissociazioneAtomizzazioneIonizzazioneEccitazioneZona di preriscaldoZona induzioneZona radiazioneZona analitica normaleFlusso nebulizzato(MX) nMXM M+
37 Ionization 80% of elements are more than 75% ionised 2040608010012056789101112131415Ionisation Energy (eV)80% of elements are more than 75% ionisedDegree of Ionisation in the ICP (%)High temperatures achievedHigh ionization efficiencyLong residence timesSample introduced at atmospheric pressureHigh dissociation efficiency
39 Sample Introduction – Layers and Jets Area of Sampling ConeArea of Skimmer ConeThe shape and diameter of thesample cone ensure correct penetrationinto the boundary layer to allow samplingof the supersonic jetSupersonicconstituents only
40 Optimisation The supersonic ion beam is now Increasing vacuumThe supersonic ion beam is nowoptimised and accelerated along the axis.
41 NEW XSeriesII Interfacce XtInterfaccia standardIdeale per alte e basse concentrazioniEccellente controllo specie poliatomicheXsInterfaccia opzionaleAlta sensibilitàBasso BECDedicato ad applicazioni per semicon
42 Plasma Sampling Interface Optimized interface geometryPatented sample & skimmer cone design- Large orifices 1.1mm & 0.75mm- Resist clogging- Highly resistant to matrix deposition- Low frequency of cleaningQuick release cone configurationTailored interface options- Xt Interface as standard- Xs interface optionPlasma Sampling InterfaceOptimized interface geometryThe X-Series interface geometry has been optimized to provide high reliability and trouble free of operation.Patented sample & skimmer cone designThe cones are manufactured from Ni with a special patented design that prevents condensation of matrix material onto the cones. This makes them very robust and ensures minimum cone maintenance and cleaning are required.—Quick release cone configurationThe sample and skimmer cones are quickly replaced using a magnetic cone tool provided with the instrument. The sample cone has a large angled collar to channel any condensed solution away from the front interface plate – for enhanced corrosion resistanceTailored interface options are available for differing applicationsThe Xt interface is provided as standard and a Xs interface is optionally available for applications that require higher sensitivity.The body of the Xt skimmer cone is made of a composite material with a pure Ni tip and the cone is mounted on a special alloy base plate. During normal operation this creates a temperature gradient along the body of the cone with the result that tip of the cone runs hot The temperature is ~ several hundred degrees – hot enough to prevent condensation of sample matrix without causing deformation of the Ni tip.
43 Infinity Lens & Protective Ion Extraction Optics Hexapole ion guide provides RF focusing and the chicane deflector provides an offset between the Infinity Ion lens and the quadrupole analyser leading to very low continuum background.Protective Ion Extraction controls the ions entering the Infinity Ion lens so only ions generated in the ICP plasma with optimised energy enter the lens region – this results in improved BECs in both CCT and non-CCT modeInfinity Lens & Protective Ion Extraction OpticsIons are sampled from the ICP plasma through the sample and skimmer cone simply by differential pressure – go from atmosphere to sub atmospheric pressure.They are then extracted by the extraction lens and focused by the Pi Extraction optics the into the Infinity Ion lensThe new Extraction optics ensure that only ions generated in the plasma pass through to the Infinity Ion Lens rejecting any ions that might have originated from the torch or have been sputtered off the skimmer cone minimizing the BEC for Gp I, Gp II and transition metalsRF only fields are applied to the hexapole rods and these focus the ion beam and transmits the focused beam onto the entrance aperture of the quadrupole via the chicane deflector.This results in the quad and the detector being mounted off axis to the ICP source – hence we get extremely low backgrounds without needing a photon stop in the ion beam that will become contaminated with high matrix samples.Including the hexapole ion lens in the basic instrument design enables us simply to add a gas manifold and 2 MFCs to bleed in the CCT gases to convert the instrument to a collision cell instrument. Hence when we do this the normal mode sensitivity is maintained. There is no compromise to the background or sensitivity spec when the collision cell option is added and this is a USP.As can be seen the ion lens is set well back from the sample cone and so doesn’t become contaminated – any cleaning required is limited to the sample and skimmer cone and extraction lens. These are mounted in front of the slide valve and can be easily removed without the need to vent the spectrometer.The extraction lens is a simple tubular design – very robust and can be cleaned either in- situ (wiping the inside with a cotton bud) or easily removed, soaked and replaced again without venting the analyser.The Ion lens and optics are located behind the slide valve & require no cleaning by the user
44 Lenti Infinity – Guide ioniche ad alta efficienza Rapida estrazione, montate in un unico modulo; esenti da manutenzioneIl migliore rapporto/rumore di qualsiasi altro ICP-MS quadrupolare (minore di <1cps random background)Ottimizzazione interattiva o totalmente automaticaEccellente tolleranza alla matrice per una migliore stabilità a lungo termine e massima efficienza di analisi tra una calibrazione e l’altraEspandibile in campo con cella di collisione CCTED della terza generazioneInfinity Lens – High Efficiency Ion GuideQuick release, single piece, maintenance free designThis slide shows the ease of access to the Infinity Ion Lens – single piece plug-in design.Highest signal-to-noise ratio of any quadrupole based ICP-MS (typically <0.5cps random background)The Infinity Ion Lens consists of a high efficiency hexapole ion guide with chicane deflector that provides the extremely low background <1 cps and high transmission > 60 MHz/ppm mid mass providing the best S/N available of any commercially available quadrupole ICP-MS.Simple interactive or fully automated optimizationIon Lens tuning can be provided entirely automatically or via interactive tuning with real time display of user defined analyte and potential interferant masses displayed on the computer VDU. (Up to 16 isotope and 4 ratios)Excellent matrix tolerance for superior long term stability and maximum sample throughput between calibrationsThe excellent ion focusing means that the lens is extremely resistant to contamination providing excellent long-term stability and minimum contamination.Field upgradeable with our second generation Collision Cell Technology – CCTEDIt can be easily upgraded to CCT technology in the field with a “plug in module” – ½ day installation
45 Lenti elettrostatiche OTTIMIZZAZIONEDiffusione degli ioni oltre lo Skimmer coneDiffusione degli ioni oltre lo skimmer coneInterfaceIon OpticsLenti elettrostaticheTorr1 TorrFlusso ionicoSkimmerPhoton Stop+Sampler+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++High Masses+Mid MassesLow MassesFotoni especie neutre
47 FiltrationAt this stage the aim is to allow at any one moment in time, a single ionto pass along the axis to the detector.The potential of one rod pair is switched with the other rod pair in such a manner that the ions move in a circular trajectory down the rod axis - The conditions at any one moment are set to only suit one ion/isotope.
49 + Volts - Pole pairs Horizontal Pole Pair Resultant Voltage arising from -DC offset & RF oscillationVertical Pole PairResultant Voltage arising from +DC offset & RF oscillation
50 + - + Mass to charge ratio The Quadrupole filters out ions of a specific mass to charge ratio.+-+
51 RF vs Voltage DC Offset RF Area inside represents Ion transmission For a given Ion mass, we can directly plot - RF vs. VoltageStability in only one axisDCOffsetRFArea inside represents Ion transmission
62 ANALIZZATORE DI MASSA + Separazione degli ioni t+D ’t t+Dt t m1/zm2 /zm3 /zQuadrupoleRisoluzione: definizioniCapacità di separare differenti masseSi definisce come l’ampiezza del picco a 5% o 10% dell’altezza del piccoRisoluzione può variare tra 0,2 e 3 amuLa sensibilità è sacrificata per la risoluzioneIl quadrupolo lavora ad una risoluzione di 0,2-1,0 amu
63 ICP-MS Quadrupole MS Abundance Sensitivity Measure of signal due to analyte at one mass higher and one mass lower than analyteAbundance sensitivity typically > 1e6 at M-1 and 1e7 at M+1
70 Detector Response for Indium Analog detector Log Counts per second 0.1ppt10ppt1ppb100ppb10ppm1000ppmConcentration0.00010.01110010,000Response cpsResponse for IndiumLog Countsper secondPulse counting detector0.11100.11100.11101001000pptppbppmConcentration
71 Dead time correction Counts Conc. Dead time correction Corrected countsActual countsPC not usable in this rangeCountsConc.
72 Sistema di rivelazione ad alte prestazioni Range dinamico lineare > 8 ordini di grandezzaSistema intelligente di protezione dalle sovraesposizioniSistema di calibrazione incrociato completamente automatico per garantire una superiore linearitàAvanzata elettronica di conteggio analogica a rapida commutazioneBa at 7ppmHigh Performance Detector System> 8 orders of magnitude dynamic rangeIntelligent over-range protectionFully automated detector cross calibration providing superior linearityAdvanced fast switching analog counting electronicsThe new X Series ICP-MS has extremely fast analog to digital conversion electronics with unprecedented signal to noise for the analog stage of the detector. This leads to a cross calibration that is not only much more accurate than previously achievable with traditional electronics but also much more stable with time. A new propriety design for converting the pulse counting signal into a data stream has lead to detector plateaus that are much flatter than previously achieved, even on an aged detector. This leads to much- improved long term signal stability and cross calibration stability between detector modes.The graphs illustrate the excellent detector cross calibration across the Ba isotopes varying from 0.1 to >70% abundance plus fast recovery following a detector trip into analogue mode.Pulse CountingAnalog