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1 The world leader in serving science 2013 ACS Spring Meeting Workshop Art Fitchett and Fergus Keenan Advances in Trace Element Analysis.

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Presentation on theme: "1 The world leader in serving science 2013 ACS Spring Meeting Workshop Art Fitchett and Fergus Keenan Advances in Trace Element Analysis."— Presentation transcript:

1 1 The world leader in serving science 2013 ACS Spring Meeting Workshop Art Fitchett and Fergus Keenan Advances in Trace Element Analysis

2 2 Agenda Ion Chromatography (IC) High Pressure Ion Chromatography (HPIC) Inductively Coupled Plasma (ICP) ICP-OES ICP-MS IC-ICP-MS Speciation

3 3 Why High Pressure Ion Chromatography Remember UHPLC? As the particle size decreases from 8µm to 4µm, column efficiency doubles This drop in particle size increases the column pressure by 4x Like HPLC, IC is moving toward smaller particle column technology HPIC Instrumentation can now handle the pressure of these smaller particle columns, even at higher flow rates.

4 4 HPIC Theory 100 Theoretical Plate Height [µm] Linear Velocity u [mm/s] Column pressure [bar] Linear Velocity u [mm/s] 10 µm particles Influence of the Particle Diameter on Pressure and Efficiency Faster Flows for Faster Separations generate Higher Pressure 5 µm particles 3 µm particles 2 µm particles Smaller Particles for Higher Efficiency generate Higher Pressure Optimal flow rate for maximum separation efficiency / resolution

5 5 HPIC System Specifications Format CapillaryMicroboreStandard Bore Flow Rate Range mL/min in µL/min increments Typical range: 5-20 µL/min mL/min in µL/min increments Typical range: mL/min mL/min in µL/min increments Typical range: 1-2 mL/min Max. Pressure 5000 psi (eluent generation) 6000 psi (pump pressure range) Column i.d.s Supported mm1-3 mm3-7 mm Yearly Eluent Usage (continuous operation) 5.25 L (10 µL/min)131L (0.25 mL/min)525 L (1 mL/min)

6 6 HPIC System Advantage HPIC systems + 4 µm particle-size columns deliver significant performance advantages Smaller resin particle columns Produce more efficient peaks Impact chromatographic speed and resolution Easier integration – more accurate and reliable results Increase sample throughput without compromising data quality Improved quality of analytical results

7 7 High Resolution using the Dionex IonPac AS11-HC-4µm Minutes µS High Resolution using the Dionex IonPac CS19-4µm Minutes Fast Run using the Dionex IonPac AS18-4µm µS Minutes Improved Resolution Provides Faster Runs and Better Results Ion-exchange columns with 4 µm particle-size Benefits Smaller particles provide better performance Faster run times with higher flow rates using 150 mm columns Better resolution with standard flow rates using 250 mm columns Applications Anions in environmental waters Organic acids in foods and beverages Amines in chemical process solutions SEM Image of 4 µm Supermacroporous Bead 4 µm New High Efficiency Dionex IonPac 4µm IC Columns in Analytical and Capillary Formats

8 8 Improved Separations using 4 µm Particle Size Capillary Columns Peaks: mg/Lmg/L 1. Quinate Bromide Fluoride Nitrate Lactate Carbonate Acetate Malonate Propionate Maleate Formate Sulfate Butyrate Oxalate Methylsulfonate Tungstate Pyruvate Phosphate Valerate Phthalate Monochloro Citrate10.0 acetate 27. Chromate Bromate cis-Aconitate Chloride trans-Aconitate Nitrite Trifluoroacetate 5.0 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 min Flow Rate:15 µL/min Inj. Volume:0.40 µL Temperature:30 °C Detection:Suppressed conductivity, Thermo Scientific Dionex ACES 300 Anion Capillary Electrolytic Suppressor, recycle mode µS Minutes Dionex IonPac AG11-HC/AS11-HC Thermo Scientific Dionex IonPac AG11-HC-4µm/AS11-HC-4µm 3600 psi 2200 psi µS

9 9 Faster Run Times without Sacrificing Resolution Column:Dionex IonPac AS18-4µm, 0.4 × 150 mm Eluent Source:Dionex EGC-KOH (Capillary) Eluent: 30 mM KOH Col. Temp.:30 °C Inj. Volume: 0.4 µL Detection:Suppressed Conductivity, Dionex ACES 300 Peaks:1. Fluoride 0.2 mg/L 2. Chloride1 3. Nitrite1 4. Sulfate1 5. Bromide1 6. Nitrate1 7. Phosphate2 Inorganic anions separation using a 4 µm capillary column 10 µL/min, 1140 psi 10 µS Minutes 5 15 µL/min, 1570 psi 25 µL/min, 2430 psi 20 µL/min, 2030 psi 30 µL/min, 2820 psi

10 10 Fast Run on the Dionex IonPac AS18-4µm Column µS Minutes Column: Dionex IonPac AS18-4µm, 0.4 × 250 mm Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 35 mM KOH Flow Rate: 30 µL/min Inj. Volume: 0.4 µL Col. Temp.: 30 °C IC Cube Temp.: 15 C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Peaks: 1. Fluoride 0.2 mg/L (ppm) 2. Chloride Nitrite Sulfate Bromide Nitrate Phosphate2.0

11 11 Column:Dionex IonPac AS18-4µm, mm Instrument:Thermo Scientific Dionex ICS HPIC System Eluent Source:Dionex EGC 500 KOH Eluent:23 mM Potassium hydroxide Flow Rate: 0.25, 0.40, 0.45, and 0.50 mL/min Inj. Volume:5 µL Column Temp.:30 °C Detection: Thermo Scientific Dionex ASRS 300 Anion Self-Regenerating Suppressor, 2 mm, recycle Peaks:1. Fluoride0.5mg/L 2. Chlorite Chloride Nitrite Carbonate Bromide Sulfate Nitrate Chlorate Minutes µS Faster Run Times without Sacrificing Resolution mL/min, 2200 psi 0.40 mL/min, 3300 psi 0.45 mL/min,3800 psi 0.50 mL/min, 4200 psi Inorganic anions separation using a 4 µm Microbore column

12 12 Isocratic Separation of Common Anions Using the Dionex IonPac AS18-4µm Column (4 ×150 mm) at Various Flow Rates Column: Dionex IonPac AG18-4µm/AS18-4um (4 × 150 mm) Eluent: 23 mM KOH Eluent Source: Dionex EGC III KOH Cartridge Flow Rate: See chromatograms Inj. Volume: 10 µL Temperature: 30 °C Detection: Suppressed conductivity, Dionex ASRS 300, AutoSuppression, recycle mode Peaks: 1.Fluoride 0.5 mg/L 2.Chlorite5 3.Chloride 3 4.Nitrite 5 5.Carbonate20 6. Bromide10 7.Sulfate Nitrate Chlorate mL/min 3332 psi µS Minutes µS Minutes µS Minutes mL/min 2574 psi 1.5 mL/min 3891 psi Inorganic anions separation using a 4 µm Standard bore column

13 13 Column:Dionex IonPac AS18-4µm, mm Instrument:Dionex ICS HPIC system Eluent Source:Dionex EGC 500 KOH Eluent:23 mM Potassium hydroxide Flow Rate: 0.50 mL/min Inj. Volume:5 µL Column Temp.:30 °C Detection:Dionex ASRS 300, 2 mm, 15 mA, recycle Sample:Municipal City A Sample Prep.:5-fold dilution with deionized water Peaks:1. Fluoride0.4mg/L 2. Chloride Nitrite< Carbonate Sulfate Nitrate< Chlorate< 0.1 Fast Analysis of Drinking Water Using High-Pressure IC 01 Minutes µS

14 14 High Resolution Cation Analysis on IonPac CS16 at Different Flow Rates Minutes µS AA B Column:IonPac CS16, 2 x 250 mm x 0.5 mm ID Eluant: 30 mmol/L MSA (EG) Flow rate:A: 10 µL/min B: 20 µL/min C: 30 µL/min Inj. volume:0.4 µL Temperature:40 °C Detection:Suppressed conductivity CCES 300, AutoSuppression, Recycle mode Peaks:1. Lithium 0.5 mg/L 2. Sodium Ammonium Potassium Magnesium Calcium C 10 µL/min 1200 psi 20 µL/min 2400 psi 30 µL/min 3600 psi

15 15 Capabilities of HPIC in Capillary Format Increased Capabilities: Faster separations with higher flow rates (left) Higher resolution with longer columns (right) µS , B 24 µL/min – 3900 psi Minutes µS Two Dionex IonPac CS16 CS16 in series Single Dionex IonPac CS16 Minutes Thermo Scientific Dionex IonSwift MAX-100: 11 minutes 10000:1 Na : Ammonia

16 16 Using HPIC to Identify Spoilage in Beverages Column:Dionex IonPac AS11-HC-4µm Capillary ( mm) Eluent Source:Dionex EGC-KOH (Capillary) Gradient:Potassium hydroxide, 1 mM from 0 to 8 min, 1-30 mM from 8-28 min, mM from min, 60 mM from min Flow Rate: 15 µL/min Inj. Volume:0.4 µL Column Temp.:30 °C Detection:Suppressed conductivity Dionex ACES 300, recycle Mode Sample Prep.:1:40 dilution with deionized water Peaks: 1. Quinate 11. Maleate 2. Fluoride 12. Sulfate 3. Lactate 13. Oxalate 4. Acetate 14. Unknown* 5. Formate 15. Phosphate 6. Unknown 16. Citrate 7. Chloride 17. cis-Aconitate 8. Unknown 18. trans-Aconitate 9. Malate-Succinate 19. Unknown 10. Carbonate Minutes µS 15 µL/min, 3600 psi

17 17 The Dionex ICS HPIC High Pressure Ion Chromatography High pressure capable with both capillary and standard flow rates Continuous operation up to 5000 psi when configured as a Reagent-Free (RFIC) system Increased productivity with fast run times Improved separations and higher resolution with 4 µm particle columns HPIC - High Resolution, Fast Analyses

18 18 Dionex ICS-4000 Capillary HPIC System Thermo Scientific Dionex IC Cube Cartridge HPIC - High Resolution, Fast Analyses Dedicated Capillary HPIC New level of resolution and speed Delivering best in class sensitivity Simplifies workflows Increases analytical efficiency and productivity Small footprint Electrochemical, Conductivity, or Charge detection

19 19 High-Pressure Ion Chromatography HPIC systems provide better performance HPIC systems allow for continuous operation up to 5000 psi HPIC systems - High-pressure ion chromatography in an all PEEK plastic IC High-pressure Reagent-Free ready Smaller 4 µm particle-size ion-exchange columns in a variety formats

20 20 The world leader in serving science Fergus Keenan Field Marketing Manager Advances in Trace Element Analysis

21 21 Agenda Advances in ICP-OES technology High speed analysis Advances in ICP-MS Intelligent Auto-dilution QCell technology Trace element speciation by IC-ICP_MS

22 22 iCAP 7600 ICP-OES Powerful analytical detection & resolution Choice of plasma orientation to enable enhanced application suitability Intelligent software for powerful auto- optimization of the sample intro system Advanced data acquisition including Sprint modes for ultimate productivity & versatility Comprehensive accessory compatibility for liquid & solid sampling Whos it for Labs requiring the extreme productivity Labs who perform highly variable & demanding research-based applications Labs who require solid sampling capability

23 23 Open Access Sample Introduction Compartment Large fully opening outer door Improved user access Clear view of plasma source Simplifies optimization Easy access to sample introduction Simple change of components Peri-pump 12 roller for smooth flow, micro tension control Better stability allows shorter dwell times Sprint Valve System Highest Sample Throughput of any ICP Drain Sensor Monitors drain, detects leaks or blockages Accessories Easy connection of Argon Humidifier, Hydride Generation and Laser Ablation accessories Better user access, compatible with all accessories

24 24 Sprint valve system – How does it work?

25 25 Sprint valve system – How does it work?

26 26 Why segmented stream? Uptake / Washout Profile with Contiguous Flow Uptake / Washout Profile with Segmented Stream Long transients Raised baseline Sharp transients Discrete washout steps True baseline

27 27 Analysis Step Time Required 1.Autosampler Movement5 sec. 2. Sample Uptake15 sec. 3. Stabilization20 sec. 4. Measurement10 sec. 5. Rinse30 sec. Total Time80 sec. – Wear Oil Analysis Case-study – Wear Oil Analysis Sprint Valve Oil Method Analysis Step Time Required 1. Autosampler Movement, Sample Uptake, Stabilization, and Rinse 17 sec. 2. Measurement10 sec. Total Time Typical Oil Method (already speed-optimized)

28 28 Intelligently Monitored Wash Software automatically detects washout to baseline for selected analytes Non-productive time reduced; analysis time optimized Washout completed sooner Maybe no wash is needed?

29 29 CASE STUDY: Ultra-Fast Agricultural Soil Analysis The soil samples were dried and ground 5 g of sample 20 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 times The total time required for these 50 repeats was 11 minutes and 35 seconds or 13.9 seconds per sample.

30 30 Ultra-Fast Agricultural Soil Analysis

31 31 Ultra-Fast Agricultural Soil Analysis

32 32 Ultra-Fast Agricultural Soil Analysis

33 33 The world leader in serving science Advances in Interference Removal in ICP-MS

34 34 iCAP Q - Dramatically Different ICP-MS

35 35 iCAP Q - Dramatically Different ICP-MS Easy to use and learn Reliability New interface cone design giving less memory effects and less drift Lower service costs and new longer life detector supplied as standard Productivity Single mode analysis capability for high throughput and quick flush times with the QCell Cost of ownership Lower gas consumption per analysis reduces running cost Longer life components (cones, detector) reduces lifetime cost Service contracts reduced by 30% over XSERIES2 Performance Best Signal /Noise of any Quadrupole ICP-MS on the Market Best interference removal with unique QCell technology New Leading Edge Design Smallest bench space requirements by unique ion optics design QCell Flatapole technology for the best in interference removal The only quadrupole MS to offer singe mode analysis

36 36 Spectral Interferences Ar, Air (O, N, C) H 2 O, Ca, Na, K, Mg, Cl, etc ArAr, ArO, ArN, ArC, ArH, ArCa, ArNa, ArK, ArMg, ArCl, ClO, NO, CO, CaO, NaO, etc ProductsReactionReactants Caused by molecular species formed in plasma overlapping with analyte isotope

37 37 Collision/Reaction Cell Technology A multipole enclosed in a cylinder Controlled flow of gas into the cell Interaction of ions with the gas If reactive gas used, reactions occur All cells are reaction cells Collision/Reaction Cell Technology M + and X n Y n + M + only out

38 38 The Basis of KED Operation 51 V + ~140 pm 51 [ClO] + ~250 pm

39 39 Increasing exit energy Bolder shades indicate higher energy for M + and MO + ions Pre-Cell Cell Post-Cell Small collision cross- section M + Larger collision cross- section MO + X Energy Barrier Key: He atom M + ion MO + ion Collisional Energy Loss and Filtering: KED

40 40 Improving Collision Cell Design QCell with low mass cut-off Flatapole technology for improved transmission Non-consumable, zero-maintenance 50% smaller volume for faster mode switching, <10s Single mode interference removal with He Can also use reactive mode with O 2, H 2 or NH 3 mixes

41 41 QCell – Low Mass Cut-Off KED mode Measuring 56 Fe QCell Mass Cut-Off Region (here all masses below 39) 1 2 3

42 42 QCell: Effect of Low Mass Cut-Off on in-cell Interference Formation

43 43 QCell Comparative Performance– He KED mode, No spike 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4

44 44 QCell Comparative Performance– He KED mode, 10ppb Spike 5%HNO 3, 5%HCl, 1%IPA, 1%H 2 SO ppb 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 Note Co sensitivity 41,000cps/ppb

45 45 QCell Comparative Performance– He KED mode, No spike 5%HNO 3, 5%HCl, 1%IPA, 1%H 2 SO 4, 200ppm Na, 200ppm Ca, 500ppm P

46 46 QCell Comparative Performance– He KED mode, 10ppb Spike 5%HNO 3, 5%HCl, 1%IPA, 1%H 2 SO 4, 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

47 47 Analysis of Selenium 78 Se Sensitivity 8441 cps/ppb IDL 5ppt 7%H 2 /He KED

48 48 Analysis of Vanadium without reactive gases 0.5% HCl, He KED mode Sensitivity 2,100 cps/ppb BEC 24ppt

49 49 Collisional Focusing for High Sensitivity Uranium Measurement Sensitivity 1223 cps/ppt IDL 16ppq Collisional focusing with 7.8mL/min He

50 50 The world leader in serving science IC-ICP-MS for Elemental Speciation

51 51 How can we Perform Speciation Analysis? SeparationDetection Thermo Scientific Dionex ICS-5000 ICThermo Scientific iCAP Q ICP-MS

52 52 Why use ICP-MS for Speciation Analysis? It can detect most of the periodic table with sub ppt detection limits It has >9 orders of magnitude linear dynamic range The (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!

53 53 What are the Advantages of Ion Chromatography? Metal-free systems Powerful separation chemistries Reagent-Free Ion Chromatography (RFIC) Extensive IC product line for full flexibility

54 54 Data System Very simple hardware connection: Simple interchange between standard ICP-MS analysis and IC-ICP-MS No need to turn off plasma A single software interface for both the IC and ICP-MS: Thermo Scientific Chromeleon interface built into workflow Fully integrated analysis No trigger cable required One sample list Inert tubing mm i.d. A Complete, Integrated IC-ICP-MS System

55 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 sample Good chromatographic resolution to separate out species Sharp peaks for improved sensitivities

56 56 iCAP Qc with Dionex ICS ppb of each As standard 6 species ~8000 cps / ppb ~15 minute analysis Anion Exchange: Dionex AS7 (2x250mm) Gradient elution with mM ammonium carbonate Flow rate: 0.3 mL/min Injection volume: 20 µL

57 57 As Species Detection Limits by IC-ICP-MS CompoundDetection limit pg g -1 AsB2.3 DMA3.8 As AsC4.4 MMA11.4 As

58 58 As Species in Apple Juice

59 59 As Speciation in Apple Juice iCAP Qc with Dionex ICS-5000: Anion exchange chromatography iCAP 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 water AsBDMAAs(III)AsCMMAAs(V)Sum of SpeciesTotal As MDL Juice 3ND 0.5 ± 0.01ND 0.7 ± ± 0.05 Juice 4ND0.4 ± ± 0.01ND0.1 ± ± ± 0.05

60 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 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 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)).

63 63 iCAP Q - Dramatically Different ICP-MS

64 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 analysis The patented QCell combines low mass filtering with Collision Reaction Cell Technology for best-in-class interference removal Ion Chromatography is for elemental speciation studies due to it inert metal free pathway and comprehensive method set for metal ion and organo-metallic separations


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