Presentation on theme: "Advances in Trace Element Analysis"— Presentation transcript:
1 Advances in Trace Element Analysis How many are familiar with HPLC?Advances in Trace Element Analysis2013 ACS Spring Meeting WorkshopArt Fitchett and Fergus Keenan
2 Agenda Ion Chromatography (IC) Inductively Coupled Plasma (ICP) High Pressure Ion Chromatography (HPIC)Inductively Coupled Plasma (ICP)ICP-OESICP-MSIC-ICP-MSSpeciation
3 Why High Pressure Ion Chromatography Remember UHPLC?As the particle size decreases from 8µm to 4µm, column efficiency doublesThis drop in particle size increases the column pressure by 4xLike HPLC, IC is moving toward smaller particle column technologyHPIC Instrumentation can now handle the pressure of these smaller particle columns, even at higher flow rates.UHPLC began the trend toward higher pressures for what reason? People wanted to run faster and save mobile phase.
4 HPIC TheoryInfluence of the Particle Diameter on Pressure and Efficiency100Column pressure [bar]20040060080010001200246810Linear Velocity u[mm/s]2 µm particles10 µm particles5 µm particles3 µm particlesTheoretical Plate Height [µm]Optimal flow rate for maximum separation efficiency / resolutionRemember the Van Deemter Equation?As the particle size decreases from 8µm to 4µm, column efficiency doublesThis drop in particle size increases the column pressure by 4xLike HPLC, IC is moving toward smaller particle column technologyHPIC Instrumentation can now handle the pressure of these smaller particle columns, but also higher flow rates.According to the van Deemter curve, the lower the H value, the higher the separation efficiency. Smaller particle sizes give low H values, ideal for fast separations on short columns.246810Linear Velocity u[mm/s]Faster Flows for Faster Separations generate Higher PressureSmaller Particles for Higher Efficiency generate Higher Pressure
5 HPIC System Specifications FormatCapillaryMicroboreStandard BoreFlow Rate RangemL/min in µL/min increments Typical range: 5-20 µL/minmL/min in µL/min increments Typical range: mL/minmL/min in µL/min increments Typical range: 1-2 mL/minMax. Pressure5000 psi (eluent generation) 6000 psi (pump pressure range)Column i.d.s Supportedmm1-3 mm3-7 mmYearly Eluent Usage (continuous operation)5.25 L (10 µL/min)131L (0.25 mL/min)525 L (1 mL/min)
6 HPIC System AdvantageHPIC systems + 4 µm particle-size columns deliver significant performance advantagesSmaller resin particle columnsProduce more efficient peaksImpact chromatographic speed and resolutionEasier integration – more accurate and reliable resultsIncrease sample throughput without compromising data qualityImproved quality of analytical resultsWe know that smaller particles provide more efficient peaks; the existing column chemistries use roughly 7-11 µm particles.The new 4 µm columns provide: the optimal combination of chromatographic speed and resolution.You can obtain more accurate and more reliable results with easier peak integrationYou can increase sample throughput without compromising data quality.The first three 4 µm capillary columns are the AS18-4 µm, which is 150 mm long, and the AS11-HC-4 µm and CS19-4 µm which are both 250 mm long.Note: Other “smaller” particle columns previously introduced AS14A (5 µm), AS15 (5 µm) and CS12A (5 µm) (3 x 150 mm).
7 Improved Resolution Provides Faster Runs and Better Results New High Efficiency Dionex IonPac 4µm IC Columns in Analytical and Capillary FormatsSEM Image of 4 µm Supermacroporous Bead4 µmIon-exchange columns with 4 µm particle-sizeBenefitsSmaller particles provide better performanceFaster run times with higher flow rates using mm columnsBetter resolution with standard flow rates using mm columnsApplicationsAnions in environmentalwatersOrganic acids in foods and beveragesAmines in chemical process solutionsHigh Resolution using theDionex IonPac AS11-HC-4µm40110MinutesµSHigh Resolution using theDionex IonPac CS19-4µm405MinutesFast Run using theDionex IonPac AS18-4µm3-0.55.5µSMinutesImproved Resolution Provides Faster Runs and Better Results
8 Improved Separations using 4 µm Particle Size Capillary Columns Eluent Source: Thermo Scientific Dionex EGC-KOH Eluent Generator Cartridge (Capillary)Gradient: Potassium hydroxide:1 mM from 0 to 5 min, 1–15 mM from 5 to 14 min, 15–30 mM from 14 to 23 min, 30–60 mM from 23 to 31 minFlow Rate: 15 µL/minInj. Volume: 0.40 µLTemperature: 30 °CDetection: Suppressed conductivity,Thermo Scientific™ Dionex™ ACES™ 300 Anion Capillary Electrolytic Suppressor, recycle mode25Thermo Scientific™ Dionex™ IonPac™ AG11-HC-4µm/AS11-HC-4µm3600 psi212220Here we demonstrate the improvement in resolution using the smaller 4 µm particle resins, comparing the IonPac AS11HC-4um in the top chromatogram and IonPac AS11HC in the larger particle size in the bottom chromatogram. There are capillary columns on the ICS HPIC system run with the sample standard and gradient conditions.The 4 µm particle column has higher peak response and more narrow peaks resulting in improved integration and reliable quantification. Lactate-Acetate, Valerate-Monochloroacetate, Bromide-Nitrate, Maleate-sulfate critical peak pairs show improved resolution (blue). Generally, reducing particle size increases the column pressure as is in this case. To achieve these separations, we must use an HPIC system, such as the Dionex ICS HPIC capillary system or the Dionex ICS-4000 Integrated HPIC capillary system.13µS178162426614122723299191125215Peaks: mg/L mg/L1. Quinate Bromide 5.02. Fluoride Nitrate 5.03. Lactate Carbonate4. Acetate Malonate 7.55. Propionate Maleate 7.56. Formate Sulfate 7.57. Butyrate Oxalate 7.58. Methylsulfonate Tungstate 10.09. Pyruvate Phosphate 10.010. Valerate Phthalate 10.011. Monochloro Citrate acetate Chromate Bromate cis-Aconitate13. Chloride trans-Aconitate 10.014. Nitrite 5.015. Trifluoroacetate 5.045710181328Dionex IonPac AG11-HC/AS11-HC2200 psiµS-1561218243036Minutes
9 Faster Run Times without Sacrificing Resolution Inorganic anions separation using a 4 µm capillary column10 µL/min, 1140 psi10µS-1520Minutes515 µL/min, 1570 psi25 µL/min, 2430 psi20 µL/min, 2030 psi30 µL/min, 2820 psi436127Column: Dionex IonPac AS18-4µm, × 150 mmEluent Source: Dionex EGC-KOH (Capillary)Eluent: 30 mM KOHCol. Temp.: 30 °CInj. Volume: 0.4 µLDetection: Suppressed Conductivity, Dionex ACES 300Peaks: 1. Fluoride mg/L2. Chloride 13. Nitrite 14. Sulfate 15. Bromide 16. Nitrate 17. Phosphate 2Here we show a similar comparison on a capillary system. The HPIC allows the use of high pressure for running higher flow rates with 4 µm columns. This column is designed to have low system back pressures for fast separations of water samples. This column, the 0.4 x 150 mm Dionex IonPac AS18-4µm column, is designed for fast separations of samples with simple matrices, such as bottled, drinking, and wastewater samples.Faster run times without sacrificing resolutionThe 0.4 x 150 mm Dionex IonPac AS18 4um column is designed for low pressure fast separations of simple sample matrices, such as drinking and wastewater sample. This flow rate can be increased to 25 uL/min, 2.5x, without the high pressure capabilities.
10 Fast Run on the Dionex IonPac AS18-4µm Column Column: Dionex IonPac AS18-4µm, 0.4 × 250 mmEluent Source: Dionex EGC-KOH Cartridge (Capillary)Eluent: 35 mM KOHFlow Rate: 30 µL/minInj. Volume: 0.4 µLCol. Temp.: 30 °CIC Cube Temp.: 15 CDetection: Suppressed conductivity,Dionex ACES 300,recycle modePeaks: Fluoride mg/L (ppm)2. Chloride 0.53. Nitrite4. Sulfate5. Bromide6. Nitrate 1.07. Phosphate 2.012345-0.55.5µSMinutes67Example of a fast run on common anions using the AS18 capillary column. 7 anions in less than 3 minutes!
11 Faster Run Times without Sacrificing Resolution Inorganic anions separation using a 4 µm Microbore column370Column: Dionex IonPac AS18-4µm, 2 150 mmInstrument: Thermo Scientific™ Dionex™ ICS HPIC™ SystemEluent Source: Dionex EGC 500 KOHEluent: 23 mM Potassium hydroxideFlow Rate: , 0.40, 0.45, and 0.50 mL/minInj. Volume: 5 µLColumn Temp.: 30 °CDetection: Thermo Scientific™ Dionex™ ASRS™ Anion Self-Regenerating Suppressor™, 2 mm, recyclePeaks: 1. Fluoride 0.5 mg/L2. Chlorite 5.03. Chloride 3.04. Nitrite 5.05. Carbonate 20.06. Bromide 10.07. Sulfate 10.08. Nitrate 10.09. Chlorate 10.074682910.50 mL/min, 4200 psi5Here we show faster run times on a 2 mm Dionex IonPac AS18-4um column. By simply doubling the flow rate, we can cut our run time in half, from 9 to 4 min.0.45 mL/min,3800 psiµS0.40 mL/min, 3300 psi0.25 mL/min, 2200 psi-20123456789Minutes
12 Inorganic anions separation using a 4 µm Standard bore column Isocratic Separation of Common Anions Using the Dionex IonPac AS18-4µm Column (4 ×150 mm) at Various Flow RatesInorganic anions separation using a 4 µm Standard bore column1.25 mL/min3332 psi246810µSMinutes135791.0 mL/min2574 psi1.5 mL/min3891 psiColumn: Dionex IonPac AG18-4µm/AS18-4um (4 × 150 mm)Eluent: mM KOHEluent Source: Dionex EGC III KOH CartridgeFlow Rate: See chromatogramsInj. Volume: 10 µLTemperature: 30 °CDetection: Suppressed conductivity,Dionex ASRS 300, AutoSuppression,recycle modePeaks: Fluoride mg/L2. Chlorite 53. Chloride4. Nitrite5. Carbonate 206. Bromide 107. Sulfate8. Nitrate9. ChlorateFigure 4I think these cgrams are different than the ones in Figure 4 in the manual because the scale is different 10 versus 6, so they need to be formatted and replace the ones in the manual. Could not confirm if these are the same as what’s in the manual now, so I reformatted them and will replace what’s in the manual now. Andy needs to confirm the pressure readings. Pressure confirmed, changed 4mm from 2574 psi to 2741 psi, the others were correct.AS18 4UM 4X150 RUNS FOR MAN 0812 SYS2 #7 [modified by AWoodruff]AS18 4UM 4X150 RUNS FOR MAN 0912 SYS2 #28AS18 4UM 4X150 RUNS FOR MAN 0912 SYS2 #23
13 Fast Analysis of Drinking Water Using High-Pressure IC Column: Dionex IonPac AS18-4µm, 2 150 mmInstrument: Dionex ICS HPIC systemEluent Source: Dionex EGC 500 KOHEluent: 23 mM Potassium hydroxideFlow Rate: mL/minInj. Volume: 5 µLColumn Temp.: 30 °CDetection: Dionex ASRS 300, 2 mm, 15 mA, recycleSample: Municipal City ASample Prep.: 5-fold dilution with deionized waterPeaks: 1. Fluoride 0.4 mg/L2. Chloride 2.33. Nitrite < 0.14. Carbonate ---5. Sulfate 3.56. Nitrate < 0.17. Chlorate < 0.11.82Here we show faster run times on a 2 mm Dionex IonPac AS18-4um column. By simply doubling the flow rate, we can cut our run time in half, from 9 to 4 min.µS5413670.812345Minutes
14 High Resolution Cation Analysis on IonPac CS16 at Different Flow Rates Column: IonPac CS16,2 x 250 mm x 0.5 mm IDEluant: 30 mmol/L MSA (EG)Flow rate: A: 10 µL/minB: 20 µL/minC: 30 µL/minInj. volume: 0.4 µLTemperature: 40 °CDetection: Suppressed conductivityCCES 300, AutoSuppression,Recycle modePeaks: 1. Lithium mg/L 2. Sodium Ammonium Potassium 5.05. Magnesium 2.56. Calcium 5.0730 µL/min 3600 psi20 µL/min 2400 psi410 µL/min 1200 psiCµS56B123A-12040Minutes14
15 Capabilities of HPIC in Capillary Format Increased Capabilities:Faster separations with higher flow rates (left)Higher resolution with longer columns (right)Capillary IC systems can now operate at higher pressures (Shipping 9/2011)Up to 5000 psi, in continuous operation, and with RFIC-EGFaster separations with higher flow rates (left)Higher resolution with longer columns (right)Thermo Scientific™ Dionex™ IonSwift™ MAX-100: 11 minutes10000:1 Na : Ammonia4.5-0.515105µS18329467111215,161913141718B24 µL/min – 3900 psiMinutesµSTwo Dionex IonPacCS16 in series16-2512Single Dionex IonPac CS16Minutes
16 Using HPIC to Identify Spoilage in Beverages 610203042Minutes12451478111816391317121915µS15 µL/min, 3600 psiColumn: Dionex IonPac AS11-HC-4µm Capillary (0.4 250 mm)Eluent Source: Dionex EGC-KOH (Capillary)Gradient: Potassium hydroxide,1 mM from 0 to 8 min, 1-30 mM from min, mM from min, 60 mM from minFlow Rate: 15 µL/minInj. Volume: 0.4 µLColumn Temp.: 30 °CDetection: Suppressed conductivityDionex ACES 300, recycle ModeSample Prep.: 1:40 dilution with deionized waterPeaks: 1. Quinate Maleate2. Fluoride Sulfate3. Lactate Oxalate4. Acetate Unknown* 5. Formate Phosphate6. Unknown Citrate7. Chloride cis-Aconitate8. Unknown trans-Aconitate9. Malate-Succinate Unknown10. CarbonateHere is an example an unintended fermentation using HPIC. A diluted orange juice sample is separated with a gradient eluent from 1 to 60 mM KOH on the capillary Dionex IonPac AS11-HC-4um column. The peaks are amazingly narrow, characteristic of this column and demonstrating the advantages of a smaller particle column. The pressure on this column is around 4000 psi and is only possible using a high pressure capillary IC system like the Dionex ICS-5000 IC. What is also interesting about this sample are peaks 3,4,6, and 9, lactate, acetate, and malate-succinate (blue). Peak 14 is also suspect, because it was not present in the fresh juice. These are fermentation products from biological activity,… evidence that this juice is spoiled.
17 The Dionex ICS-5000+ HPIC HPIC - High Resolution, Fast Analyses High Pressure Ion ChromatographyHigh pressure capable with both capillary and standard flow ratesContinuous operation up to 5000 psi when configured as a Reagent-Free (RFIC™) systemIncreased productivity with fast run timesImproved separations and higher resolution with 4 µm particle columnsAs you may know, the ICS-5000 is the worlds first capillary IC. Now we are introducing another worlds first, High Pressure IC psi may not sound like a lot in the world of HPLC, but when you consider that the ICS-5000 is a 100% polymer system (PEEK) this is quite an achievement.Developed for flexibility, modularity, and ease-of-use, the Dionex ICS HPIC™ systemcombines the highest chromatographic resolution with convenience. The Dionex ICS HPICsystem brings a new level of resolution and speed to ion chromatography analysis with high operatingpressures.HPIC - High Resolution, Fast Analyses
18 HPIC - High Resolution, Fast Analyses Dionex ICS-4000 Capillary HPIC SystemDedicated Capillary HPICNew level of resolution and speedDelivering best in class sensitivitySimplifies workflowsIncreases analytical efficiency and productivitySmall footprintElectrochemical, Conductivity, or Charge detectionThe World’s First Dedicated Capillary High-Pressure Reagent-Free Ion Chromatography systemHere we will do a short introduction to QD, charge detection, our new universal detector.Thermo Scientific™ Dionex™ IC Cube™ CartridgeHPIC - High Resolution, Fast Analyses
19 High-Pressure Ion Chromatography HPIC systems provide better performanceHPIC systems allow for continuous operation up to 5000 psiHPIC systems - High-pressure ion chromatography in an all PEEK™ plastic ICHigh-pressure Reagent-Free readySmaller 4 µm particle-size ion-exchange columns in a variety formatsHigh Pressure Ion Chromatography brings together high pressure capable Dionex IC systems, high pressure capable consumables, and smaller particle size ion exchange columns.Makes it possible to use new, smaller 4 µm particle-size ion-exchange columns in capillary and analytical scale formats. Dionex HPIC IC systems + HPIC Reagent-Free consumables + 4 µm particle-size deliver significant performance advantages
20 Advances in Trace Element Analysis Fergus KeenanField Marketing Manager
21 Agenda Advances in ICP-OES technology Advances in ICP-MS High speed analysisAdvances in ICP-MSIntelligent Auto-dilutionQCell technologyTrace element speciation by IC-ICP_MS
22 iCAP 7600 ICP-OES Powerful analytical detection & resolution Choice of plasma orientation to enable enhanced application suitabilityIntelligent software for powerful auto-optimization of the sample intro systemAdvanced data acquisition including ‘Sprint’ modes for ultimate productivity & versatilityComprehensive accessory compatibility for liquid & solid samplingWho’s it forLabs requiring the extreme productivityLabs who perform highly variable & demanding research-based applicationsLabs who require solid sampling capability
23 Open Access Sample Introduction Compartment Large fully opening outer doorImproved user accessClear view of plasma sourceSimplifies optimizationEasy access to sample introductionSimple change of componentsPeri-pump12 roller for smooth flow, micro tension controlBetter stability allows shorter dwell timesSprint Valve SystemHighest Sample Throughput of any ICPDrain SensorMonitors drain, detects leaks or blockagesAccessoriesEasy connection of Argon Humidifier, Hydride Generation and Laser Ablation accessories“Better user access, compatible with all accessories”
24 Sprint valve system – How does it work? Point out the flow paths the carrier and samplePoint out the bubbler, it will be explained in a few slides slide
25 Sprint valve system – How does it work? Point out the flow paths the carrier and samplePoint out the bubbler, it will be explained in a few slides slide
26 Uptake / Washout Profile with Contiguous Flow Why segmented stream?Uptake / Washout Profile with Contiguous FlowLong transientsRaised baselineUptake / Washout Profile with Segmented StreamDiscrete washout stepsSharp transientsTrue baseline
28 Intelligently Monitored Wash Software automatically detects washout to baseline for selected analytesNon-productive time reduced; analysis time optimizedWashout completed soonerMaybe no wash is needed?The use of an inelegant rinse can get over this problem. Based on the results of the sample analysis the iTEVA Software will instruct one of three actionsIf the results of the analysis are high (above a user set limit) then the probe will be washed until the signal falls below a user set levelIf the results are between with in a certain range the probe will be washed for a specific time (say 10 seconds)If the results are low (below a user set level) then the probe will move to the next sample.This can save a massive amount of was time and can also prevent carry over from unexpectedly high samples
29 CASE STUDY: Ultra-Fast Agricultural Soil Analysis The soil samples were dried and ground 5 g of sample20 ml of the 1M ammonium acetate solution was added.Samples shaken vigorously for at least 5 minutes and left to react overnight.Samples were then shaken again and filtered before being made up to 250 ml with de-ionized water.Sample extracts were analysed directly using the Sprint acquisition mode which further enhances the speed of the instrument.A locally sourced soil sample was extracted 5 times & each extract was analysed 10 timesThe total time required for these 50 repeats was 11 minutes and 35 seconds or 13.9 seconds per sample.
35 iCAP Q - Dramatically Different ICP-MS Easy to use and learnReliabilityNew interface cone design giving less memory effects and less driftLower service costs and new longer life detector supplied as standardProductivitySingle mode analysis capability for high throughput and quick flush times with the QCellCost of ownershipLower gas consumption per analysis reduces running costLonger life components (cones, detector) reduces lifetime costService contracts reduced by 30% over XSERIES2PerformanceBest Signal /Noise of any Quadrupole ICP-MS on the MarketBest interference removal with unique QCell technologyNew Leading Edge DesignSmallest bench space requirements by unique ion optics designQCell Flatapole technology for the best in interference removalThe only quadrupole MS to offer singe mode analysis
36 Spectral Interferences Caused by molecular species formed in plasma overlapping with analyte isotopeAr, Air(O, N, C)ArAr, ArO, ArN, ArC, ArH, ArCa, ArNa, ArK, ArMg, ArCl, ClO, NO, CO, CaO, NaO, etcH2O, Ca, Na, K, Mg, Cl, etcProducts Reaction Reactants
37 Collision/Reaction Cell Technology A multipole enclosed in a cylinderControlled flow of gas into the cellInteraction of ions with the gasIf reactive gas used, reactions occurAll cells are reaction cellsM+ only outAll CRCs consist of a multipole enclosed in a cylinder with a small entry and exit aperture to allow ions to pass into and out of the cell. The exact design depends upon the manufacturer of the instrument. The table below shows some of the major design characteristics of the three major manufacturers:Manufacturer Lens Design Multipole DrivePE/SCIEX Photon-stop Quadrupole RF/DC, frequency scanThermo Chicane deflector Hexapole RF-only, amplitude scanAgilent Off-axis Octapole RF-only, no scanThe multipole has applied fields (RF only or a combination of RF and DC) which guide the ions entering the cell along the path of the multipole, rather like the passage of ions through a quadrupole mass analyzer. Its job is to transmit ions as efficiently as possible through the cell region. When the cell is unpressurized, the system transmits ions just like a standard mass spectrometer and has performance characteristics to match.Cell instruments also have one or two mass flow controllers (MFCs) to allow controlled flow rates of reagent gas into the cell. The gas establishes an equilibrium in the cell and escapes through the entry and exit apertures to be pumped away by the vacuum system. The partial pressure of gas in the cell region is therefore directly proportional to the gas flow rate, so what we are actually controlling when we change the cell gas flow rate is the cell partial pressure. The partial pressure controls the mean free path of ions traversing the cell and therefore the rate of collision or collision number.The idea is to pressurize the cell with a gas that will produce interactions with the unwanted polyatomics that don’t happen with the analyte ions and to pressurize it just enough to remove the polyatomics by this interaction mechanism.Some manufacturers state that collision cells are different to reaction cells, but it merely depends upon what gas is used. If a reactive gas is used a reaction will occur and for that to happen, a collision must first take place. Hence, all collision cells are reaction cells and all reaction cells are collision cells.M+ and XnYn’+
38 The Basis of KED Operation 51V+ ~140 pm51[ClO]+ ~250 pm
39 Collisional Energy Loss and Filtering: KED Energy BarrierCellPre-CellPost-CellSmall collision cross-section M+Larger collision cross-section MO+XThis slide is designed to illustrate how energy discrimination works. It is merely an illustration and it not intended to be an accurate representation of the actual number of collisions or processes that occur in the cell.It has been seen that using low reactivity gases, strongly bonded metal oxide species can be attenuated relative to the metal when there is apparently insufficient energy in the unreactive collisions to dissociate the species. This phenomenon is likely to be due to kinetic energy discrimination. The illustration explains how this can happen.The boxes represent the mass spectrometer, pre-cell, cell and post-cell. In this illustration the cell is pressurized with He gas.If we consider a small collision cross-section species, M+, it will enter the cell with quite a high energy. It may collide with a He atom, losing a little energy and then exit the cell.If we now consider a larger collision cross section species, MO+, it will enter the cell with a similar energy to M+. It will undergo a larger number of collisions due to its larger collision cross section and consequently it will lose more energy than M+ by the time it exits the cell.If we can induce an energy barrier, we can block MO+ from passing into the analyser, while M+ continues.The same type of process can be used to suppress the transmission of cell reaction products as these will have lower energies than unreacted ions of similar mass.Bolder shades indicate higher energy for M+ and MO+ ionsKey:He atomM+ ionMO+ ionIncreasing exit energy
40 Improving Collision Cell Design QCell with low mass cut-offFlatapole technology for improved transmissionNon-consumable, zero-maintenance50% smaller volume for faster mode switching, <10sSingle mode interference removal with HeCan also use reactive mode with O2, H2 or NH3 mixes
41 QCell – Low Mass Cut-Off KED mode QCell Mass Cut-Off Region (here all masses below 39)2Measuring 56Fe31
42 QCell: Effect of Low Mass Cut-Off on in-cell Interference Formation
43 QCell Comparative Performance– He KED mode, No spike 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4
44 QCell Comparative Performance– He KED mode, 10ppb Spike 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4+ 10ppb Spike of Li, Be, B, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Ni, Cu, Zn, Ga, Ge, As, SeNote Co sensitivity 41,000cps/ppb
45 QCell Comparative Performance– He KED mode, No spike 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4, 200ppm Na, 200ppm Ca, 500ppm P
46 QCell Comparative Performance– He KED mode, 10ppb Spike 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4, 200ppm Na, 200ppm Ca, 500ppm P+ 10ppb Spike of Li, Be, B, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Ni, Cu, Zn, Ga, Ge, As, Se
48 Analysis of Vanadium without reactive gases Sensitivity 2,100 cps/ppbBEC 24ppt0.5% HCl, He KED mode
49 Collisional Focusing for High Sensitivity Uranium Measurement Sensitivity 1223 cps/pptIDL 16ppqCollisional focusing with 7.8mL/min He
50 IC-ICP-MS for Elemental Speciation I’m now going to change subject slightly and talk about the application of ICP-MS in combination with IC – Ion Chromatography – for the elemental speciation analysis of pharmaceutical productsIC-ICP-MS for Elemental Speciation
51 How can we Perform Speciation Analysis? SeparationDetectionNow that we understand why speciation analysis has to be considered as part of USP, the next question to answer is how can we perform it ? The answer is very simple, we need a separation technique and a detector. The chromatographic system is used to separate the different chemical species and the ICP-MS – in real time – detects and quantifies the elemental concentration of each of the individual species coming from the chromatographic separation. The most common chromatography is some form of liquid chromatography or ion chromatography.Thermo Scientific Dionex ICS-5000 ICThermo Scientific iCAP Q ICP-MS
52 Why use ICP-MS for Speciation Analysis? It can detect most of the periodic table with sub ppt detection limitsIt has >9 orders of magnitude linear dynamic rangeThe (atmospheric, ground potential) ICP ion source is easily connected to a wide range of coupled accessories:Ion Chromatography (IC); Gas Chromatography (GC); High performance liquid chromatography (HPLC)…ICP-MS is the ideal elemental detector for speciation analysis!Existing USP methods describe wet chemical and AAS based methods for the determination of inorganic arsenic and mercury. The most commonly used technique for speciation currently however is the combination of a separation system with ICP-MS and this is ideally suited to USP 232’s requirements for speciation analysis. ICP-OES can be used as a detector for separation techniques but due to its lower instrumental sensitivity – especially for As and Hg – its application in real world speciation analyses is limited since we are detecting individual components of an element and not the total concentration.ICP-MS however provides accurate high quality data with pg/ml or sub pg/ml detection limits for many analytes, including As and Hg. The iCAP Q ICP-MS with its bench height, open sample introduction system is easily connected to a range of separation techniques – not just Ion Chromatography but also Gas and High Performance Liquid Chromatographic – making it the ideal elemental detector for speciation analyses.
53 What are the Advantages of Ion Chromatography? Metal-free systemsPowerful separation chemistriesReagent-Free Ion Chromatography (RFIC)Extensive IC product line for full flexibilityIon chromatography is a mature, well developed technique. The principles of ion separation are well understood, easy to control and applications and columns dedicated to specific species are widely available. More importantly for the metal speciation applications required by USP is that the Thermo Scientific Dionex IC systems are totally metal free. With metal free pumps and metal free pathways there is no contamination of the sample from the chromatographic system itself. Reagent free ion chromatography systems are available where a dedicated cartridge supplies the anionic or cation eluent needed for the chromatographic separation removing the need for manual preparation, increasing ease of use. The IC product line from Thermo Scientific Dionex is extensive and speciation solutions for arsenic and mercury are available in tailored, off-the-shelf configurations.
54 A Complete, Integrated IC-ICP-MS System Very simple hardware connection:Simple interchange between standard ICP-MS analysis and IC-ICP-MSNo need to turn off plasmaA single software interface for both the IC and ICP-MS:Thermo Scientific Chromeleon interface built into workflowFully integrated analysisNo trigger cable requiredOne sample listInert tubing mm i.d.A very simple hardware connection is required between the IC and the ICP-MS: a short section of narrow ID inert tubing connects the outlet of the IC column directly to the ICP-MS nebulizer.It is not even necessary to turn the plasma off when the changing between total elemental and speciation analysis modes!The Thermo Scientific IC-ICP-MS system uses a single software interface for control of both the IC and the ICP-MS. Chromeleon, a well known chromatography software is fully integrated within the ICP-MS software, Qtegra, so that both systems can be controlled from within one user interface working from a single sample list. No trigger cable is required and routine, unattended sequences are easily created and processed.DataSystem
55 Speciation of As in Apple Juice Differentiation between (toxic) inorganic As(III) & As(V) species and (non-toxic) organic species (MMA etc)Requirements:Single run anionic and cationic technique since both positive and negative charged species can be present in a sampleGood chromatographic resolution to separate out speciesSharp peaks for improved sensitivities
56 iCAP Qc with Dionex ICS-5000 0.45 ppb of each As standard6 species~8000 cps / ppb~15 minute analysisAnion Exchange:Dionex AS7 (2x250mm)Gradient elution with mM ammonium carbonateFlow rate: 0.3 mL/minInjection volume: 20 µL
57 As Species Detection Limits by IC-ICP-MS CompoundDetection limit pg g-1AsB2.3DMA3.8As3+4.6AsC4.4MMA11.4As5+1.2
59 As Speciation in Apple Juice iCAP Qc with Dionex ICS-5000:Anion exchange chromatographyiCAP Qc benefits:Low method detection limits: and 0.01 ng/g per species, ng/g total As vs current EPA MCL (maximum contaminant level) is 10 ng/g in drinking waterAsBDMAAs(III)AsCMMAAs(V)Sum of SpeciesTotal AsMDL0.0020.0040.0050.0110.001-Juice 3ND0.5 ± 0.010.7 ± 0.011.21.7 ± 0.05Juice 40.4 ± 0.050.3 ± 0.010.1 ± 0.051.51.8 ± 0.05
60 IC-ICP-MS analysis of As in Organic Brown Rice Syrup Media reports and scientific publications on the determination of arsenic (As) in foodstuffs have sparked renewed interest from consumer groups and politicians leading to responses from national regulatory bodies.Following the publication of a report on high As levels in organic brown rise syrup the United State Food and Drug Administration (FDA) stated that it was carrying out a study on As in rice and rice products that is due to report later in 2012.
61 Analysis of As in rice syrup Three different OBRS samples were sourced and prepared for analysis.A closed microwave digestion method was used.Preparation of the OBRS samples for As speciation analysis was achieved by taking 1.5 g of OBRS, adding 15 mL of 0.28 M HNO3 and refluxing for 90 minutes.
62 Speciation of As in OBRS IC-ICP-MS speciation analysis showed that the predominant As species in the OBRS samples tested was the toxic inorganic As(III) with over 80% of the total arsenic concentration(equivalent to 86 – 109 ng /g As (III)).
64 Summary iCAP 7600 is the fastest ICP-OES system available With the iCAP Q ICP-MS is completely automated from standard prep to sample dilution and automated interference free analysisThe patented QCell combines low mass filtering with Collision Reaction Cell Technology for best-in-class interference removalIon Chromatography is for elemental speciation studies due to it inert metal free pathway and comprehensive method set for metal ion and organo-metallic separations