1. Advances in Trace Element Analysis
How many are familiar with HPLC?
Advances in Trace Element Analysis
2013 ACS Spring Meeting Workshop
Art Fitchett and Fergus Keenan

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

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.
UHPLC began the trend toward higher pressures for what reason? People wanted to run faster and save mobile phase.

4. HPIC Theory
Influence of the Particle Diameter on Pressure and Efficiency
100
Column pressure [bar]
200
400
600
800
1000
1200 2 4 6 8 10
Linear Velocity u
[mm/s]
2 µm particles
10 µm particles
5 µm particles
3 µm particles
Theoretical Plate Height [µm]
Optimal flow rate for maximum separation efficiency / resolution
Remember the Van Deemter Equation?
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, 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. 2 4 6 8 10
Linear Velocity u
[mm/s]
Faster Flows for Faster Separations generate Higher Pressure
Smaller Particles for Higher Efficiency generate Higher Pressure

5. HPIC System Specifications
Format
Capillary
Microbore
Standard 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 mm
1-3 mm
3-7 mm
Yearly Eluent Usage (continuous operation)
5.25 L (10 µL/min)
131L (0.25 mL/min)
525 L (1 mL/min)

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
We 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 integration
You 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 Formats
SEM Image of 4 µm Supermacroporous Bead
4 µm
Ion-exchange columns with 4 µm particle-size
Benefits
Smaller particles provide better performance
Faster run times with higher flow rates using mm columns
Better resolution with standard flow rates using mm columns
Applications
Anions in environmental
waters
Organic acids in foods and beverages
Amines in chemical process solutions
High Resolution using the
Dionex IonPac AS11-HC-4µm 40 1 10
Minutes µS
High Resolution using the
Dionex IonPac CS19-4µm 40 5
Minutes
Fast Run using the
Dionex IonPac AS18-4µm 3
-0.5
5.5 µS
Minutes
Improved 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 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 25
Thermo Scientific™ Dionex™ IonPac™ AG11-HC-4µm/AS11-HC-4µm
3600 psi 21 22 20
Here 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. 13 µS 17 8 16 24 26 6 14 12 27 23 29 9 19 11 25 2 15
Peaks: mg/L mg/L
1. Quinate Bromide 5.0
2. Fluoride Nitrate 5.0
3. Lactate Carbonate
4. Acetate Malonate 7.5
5. Propionate Maleate 7.5
6. Formate Sulfate 7.5
7. Butyrate Oxalate 7.5
8. Methylsulfonate Tungstate 10.0
9. Pyruvate Phosphate 10.0
10. Valerate Phthalate 10.0
11. Monochloro Citrate acetate Chromate Bromate cis-Aconitate
13. Chloride trans-Aconitate 10.0
14. Nitrite 5.0
15. Trifluoroacetate 5.0 4 5 7 10 18 1 3 28
Dionex IonPac AG11-HC/AS11-HC
2200 psi µS
-15 6 12 18 24 30 36
Minutes

9. Faster Run Times without Sacrificing Resolution
Inorganic anions separation using a 4 µm capillary column
10 µL/min, 1140 psi 10 µS
-15 20
Minutes 5
15 µL/min, 1570 psi
25 µL/min, 2430 psi
20 µL/min, 2030 psi
30 µL/min, 2820 psi 4 3 6 1 2 7
Column: Dionex IonPac AS18-4µm, × 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 mg/L
2. Chloride 1
3. Nitrite 1
4. Sulfate 1
5. Bromide 1
6. Nitrate 1
7. Phosphate 2
Here 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 resolution
The 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 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: Fluoride mg/L (ppm)
2. Chloride 0.5
3. Nitrite
4. Sulfate
5. Bromide
6. Nitrate 1.0
7. Phosphate 2.0 1 2 3 4 5
-0.5
5.5 µS
Minutes 6 7
Example 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 column 3 70
Column: Dionex IonPac AS18-4µm, 2 150 mm
Instrument: Thermo Scientific™ Dionex™ ICS HPIC™ System
Eluent Source: Dionex EGC 500 KOH
Eluent: 23 mM Potassium hydroxide
Flow Rate: , 0.40, 0.45, and 0.50 mL/min
Inj. Volume: 5 µL
Column Temp.: 30 °C
Detection: Thermo Scientific™ Dionex™ ASRS™ Anion Self-Regenerating Suppressor™, 2 mm, recycle
Peaks: 1. Fluoride 0.5 mg/L
2. Chlorite 5.0
3. Chloride 3.0
4. Nitrite 5.0
5. Carbonate 20.0
6. Bromide 10.0
7. Sulfate 10.0
8. Nitrate 10.0
9. Chlorate 10.0 7 4 6 8 2 9 1
0.50 mL/min, 4200 psi 5
Here 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 psi µS
0.40 mL/min, 3300 psi
0.25 mL/min, 2200 psi
-20 1 2 3 4 5 6 7 8 9
Minutes

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 Rates
Inorganic anions separation using a 4 µm Standard bore column
1.25 mL/min
3332 psi 2 4 6 8 10 µS
Minutes 1 3 5 7 9
1.0 mL/min
2574 psi
1.5 mL/min
3891 psi
Column: Dionex IonPac AG18-4µm/AS18-4um (4 × 150 mm)
Eluent: 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: Fluoride mg/L
2. Chlorite 5
3. Chloride
4. Nitrite
5. Carbonate 20
6. Bromide 10
7. Sulfate
8. Nitrate
9. Chlorate
Figure 4
I 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 #28
AS18 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 mm
Instrument: Dionex ICS HPIC system
Eluent Source: Dionex EGC 500 KOH
Eluent: 23 mM Potassium hydroxide
Flow Rate: 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. Fluoride 0.4 mg/L
2. Chloride 2.3
3. Nitrite < 0.1
4. Carbonate ---
5. Sulfate 3.5
6. Nitrate < 0.1
7. Chlorate < 0.1
1.8 2
Here 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. µS 5 4 1 3 6 7
0.8 1 2 3 4 5
Minutes

14. High Resolution Cation Analysis on IonPac CS16 at Different Flow Rates
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 mg/L 2. Sodium Ammonium Potassium 5.0
5. Magnesium 2.5
6. Calcium 5.0 7
30 µL/min 3600 psi
20 µL/min 2400 psi 4
10 µL/min 1200 psi C µS 5 6 B 1 2 3 A -1 20 40
Minutes 14

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-EG
Faster separations with higher flow rates (left)
Higher resolution with longer columns (right)
Thermo Scientific™ Dionex™ IonSwift™ MAX-100: 11 minutes
10000:1 Na : Ammonia
4.5
-0.5 15 10 5 µS 1 8 3 2 9 4 6 7 11 12
15,16 19 13 14 17 18 B
24 µL/min – 3900 psi
Minutes µS
Two Dionex IonPac
CS16 in series 16 -2 5 1 2
Single Dionex IonPac CS16
Minutes

16. Using HPIC to Identify Spoilage in Beverages6 10 20 30 42
Minutes 1 2 4 5 14 7 8 11 18 16 3 9 13 17 12 19 15 µS
15 µL/min, 3600 psi
Column: 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 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 Maleate
2. Fluoride Sulfate
3. Lactate  Oxalate
4. Acetate  Unknown* 
5. Formate Phosphate
6. Unknown Citrate
7. Chloride cis-Aconitate
8. Unknown trans-Aconitate
9. Malate-Succinate Unknown
10. Carbonate
Here 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 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
As 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™ system
combines the highest chromatographic resolution with convenience. The Dionex ICS HPIC
system brings a new level of resolution and speed to ion chromatography analysis with high operating
pressures.
HPIC - High Resolution, Fast Analyses

18. HPIC - High Resolution, Fast Analyses
Dionex ICS-4000 Capillary HPIC System
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
The World’s First Dedicated Capillary High-Pressure Reagent-Free Ion Chromatography system
Here we will do a short introduction to QD, charge detection, our new universal detector.
Thermo Scientific™ Dionex™ IC Cube™ Cartridge
HPIC - High Resolution, Fast Analyses

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
High 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 Keenan
Field Marketing Manager

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

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
Who’s it for
Labs requiring the extreme productivity
Labs who perform highly variable & demanding research-based applications
Labs who require solid sampling capability

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. Sprint valve system – How does it work?
Point out the flow paths the carrier and sample
Point 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 sample
Point 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 Flow
Long transients
Raised baseline
Uptake / Washout Profile with Segmented Stream
Discrete washout steps
Sharp transients
True baseline

27. Case-study – Wear Oil Analysis
Typical Oil Method
(already speed-optimized)
Sprint Valve Oil Method
Analysis Step
Time Required
1.Autosampler Movement
5 sec.
2. Sample Uptake
15 sec.
3. Stabilization
20 sec.
4. Measurement
10 sec.
5. Rinse
30 sec.
Total Time
80 sec.
Analysis Step
Time Required
1. Autosampler Movement, Sample Uptake, Stabilization, and Rinse
17 sec.
2. Measurement
10 sec.
Total Time
27 sec.

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?
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 actions
If 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 level
If 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 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. Ultra-Fast Agricultural Soil Analysis

31. Ultra-Fast Agricultural Soil Analysis

32. Ultra-Fast Agricultural Soil Analysis

33. Advances in Interference Removal in ICP-MS

34. iCAP Q - Dramatically Different ICP-MS

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. Spectral Interferences
Caused by molecular species formed in plasma overlapping with analyte isotope
Ar, Air
(O, N, C)
ArAr, ArO, ArN, ArC, ArH, ArCa, ArNa, ArK, ArMg, ArCl, ClO, NO, CO, CaO, NaO, etc
H2O, Ca, Na, K, Mg, Cl, etc
Products Reaction Reactants

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
M+ only out
All 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 Drive
PE/SCIEX Photon-stop Quadrupole RF/DC, frequency scan
Thermo Chicane deflector Hexapole RF-only, amplitude scan
Agilent Off-axis Octapole RF-only, no scan
The 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 pm
51[ClO]+ ~250 pm

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

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 O2, H2 or NH3 mixes

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

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, Se
Note 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

47. Analysis of Selenium 78Se Sensitivity 8441 cps/ppb IDL 5ppt
7%H2/He KED

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

49. Collisional Focusing for High Sensitivity Uranium Measurement
Sensitivity 1223 cps/ppt
IDL 16ppq
Collisional 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 products
IC-ICP-MS for Elemental Speciation

51. How can we Perform Speciation Analysis?
Separation
Detection
Now 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 IC
Thermo 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 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!
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 systems
Powerful separation chemistries
Reagent-Free Ion Chromatography (RFIC)
Extensive IC product line for full flexibility
Ion 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-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 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.
Data
System

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. iCAP Qc with Dionex ICS-5000
0.45 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. As Species Detection Limits by IC-ICP-MS
Compound
Detection limit pg g-1
AsB
2.3
DMA
3.8
As3+
4.6
AsC
4.4
MMA
11.4
As5+
1.2

58. As Species in Apple Juice

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
AsB
DMA
As(III)
AsC
MMA
As(V)
Sum of Species
Total As
MDL
0.002
0.004
0.005
0.011
0.001 -
Juice 3 ND
0.5 ± 0.01
0.7 ± 0.01
1.2
1.7 ± 0.05
Juice 4
0.4 ± 0.05
0.3 ± 0.01
0.1 ± 0.05
1.5
1.8 ± 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)).

63. iCAP Q - Dramatically Different ICP-MS

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