presentatioachieving ultra fast, low cost elemental analysis
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8/8/2019 PresentatioAchieving Ultra Fast, Low Cost Elemental Analysis
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Achieving Ultra Fast, Low Cost
Elemental Analyses in Compliance with
EPA Protocols
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Polling question 1
What is your typical sample analysis time for a soil or sludge sample?
Less than 1 minute
Between 1 and 2 minutes
Greater than 2 minutes
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Todays Speakers
Matthew Cassap
Senior Application Specialist
Thermo Fisher Scientific
Jayme CuretApplications Scientist
Thermo Fisher Scientific
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Polling question 1 Results
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What will be covered
The sample introduction systems for ICP-OES and ICP-MS
Simple steps for increasing sample throughput
New developments in sample introductions systems and ICP-OES dataacquisition technology
Advanced sample introduction systems becoming routine
How these advances can be applied to your analysis High speed trend analysis
Analysis using the 6010C EPA protocol
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ICP-OES and ICP-MS
Have similar sample introduction systems which turn a liquid sample into
an aerosol
The aerosol is transported to the plasma where:
The sample is atomized and then ionized
Atoms and ions emit light
ICP-MS quantifies the concentration of an element based on the amountof ions in the sample
ICP-OES quantifies the concentration of an element based on theintensity of light emitted from an atom or ion
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Similarities in sample introduction
The purpose of the sample
introduction is to convert a liquid toan aerosol
Via a nebulizer
Typically the sample is pumped tothe nebulizer from its vessel by a
peristaltic pump
The sample is transferred to theplasma from the nebulizer via aspray chamber and transfer tube
The spray chamber removes large
droplets in the aerosol to preventplasma loading
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Limitations of sample introduction pre nebulizer
Manual movements between samples
Use of a scientist
Non consistent timings for wash and sampleuptake
Long sample uptake times
Distance from the sample probe to the nebulizer
Limited pump speed
Large amounts of sample used
Memory effects from sticky and highconcentration elements
Hg and B are considered sticky
Unexpected high concentrations can cause carryover
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Limitations of the nebulizer
Small capillaries within the nebulizer
Prone to clogging
Delicate
Samples with different physical properties create different amounts ofaerosol
Viscosity
Volatility
Too many to choose from
Is the correct nebulizer being used for solids content of the sample?
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Limitations of sample introduction post nebulizer
How efficient is the spray
chamber at removinglarge droplets
More important for ICP-MS where too muchsolvent in the plasma will
cause interferences How large is the spray
chamber
Memory effects withsticky elements
Sample introduction andwash out time
Double-Pass Spraychamber
Cyclonic Spraychamber
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Limitations of the system as a whole
Time consuming
Can be over 50% of the total sample cycle time
Wastes sample
Sample remains in uptake tubing
Typically less than 3% of the sample ends up in the plasma
Source of every day problems Poor RSDs
Poor sensitivity
Contamination
Drift
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A fully optimized sample introduction system will;
Have a short sample uptake time
Use minimal sample
Remove large droplets from the aerosol efficiently
Have minimal memory effects
Have a short sample uptake time
Be stable Resistant to blockage
And hopefully the correct result!!
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Use of an auto sampler
Will automate sample changing
Provide consistent sample timings
Sample uptake
Sample wash
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Close coupling of the auto-sampler accessory
Ensure the auto-sampler is as close to the sample introduction systemas possible and reduce sample tubing lengths.
Minimising sample uptake time
Minimising wash time
150 cm47 cm30 cm
115 cm15 cm
Typical
Minimum
Total = 227 cm
Total = 177 cm
Difference = 50 cm
Saves ~15 s per sample at 2 mL/min uptake/wash with iCAP but the principle applies to alltechniques
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Pump speed
Peristaltic pump range
Most pumps will have more thatone speed
Use different speeds for differentparts of the analysis
Normal analysis rate 50 rpm
Fast pump capability for flush
Saves up to 40 s per sample(including uptake and wash)
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Just for ICP-MS
As the ion optics and detector are in a vacuum chamber an interface is
present in the instrument Use of two cones with small orifices
Can be prone to clogging with high sample matrix
Dilution of the sample
Minimize the time the cones are exposed to the matrix
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Software optimization
The instrument software can also help to optimize the sampleintroduction time
The Thermo Scientific iTEVA Software has the following features Intelligent Rinse
Auto sampler Step A Head
Software automatically detectswashout to baseline forselected analytes
Non-productive time reduced;analysis time optimized
Washout completed sooner
Maybe no wash is needed?1
10
100
1000
10000
100000
000000
0 20 40 60 80 100 120 140 160 180
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Step-Ahead Sampling
Step-ahead autosampler control
send the autosampler probe to wash beforethe sample analysis is complete
Residual sample used to complete theanalysis
Sample line already primed with washsolution for washout
Can save more than 1 minute per sample innon-productive time
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Autosampler Step-Ahead
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Recap simple optimization
Simple steps can be taken to optimize sample introduction
Shorten all tubing lengths
Use a autosampler
Use fast sample uptake and washout pump speeds
Use a low volume spray chamber
Use the software features
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Advanced optimization of the system
Use of vacuum to load the sample very quickly on to a loop
Inject the sample from the loop in to the spray chamber
Significantly shortens sample introduction times
Reduces the amount of matrix that enters the plasma
Key for ICP-MS, this will prevent cones from clogging
Systems are commercially available and in use in routine environments
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Introducing the dual loop system
As mentioned single loop systems are used in routine labs
There is still dead time associated with this configuration
For a fully optimized system a dual loop system can be used inconjunction with the auto sampler Step A Head feature of the the iTEVASoftware.
Whilst one loop the solution from one loop is being analyzed the otherloop is being filled ready for analysis
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What happens during the analysis with two loops
ESI SC4 DX FAST iTEVA Software
Autosampler moves to sample 1
Autosampler moves to sample 2
Sample 1 flush time
Sample 1 integration
Sample 1 loaded on to loop
Sample 1 injected to nebulizer
Autosampler moves to wash
Sample 2 loaded on to loop
Sample 2 injected to nebulizer
Autosampler moves to wash
Autosampler moves to sample 3
Sample 3 loaded on to loop
Sample 3 injected to nebulizer
Autosampler moves to wash
Sample 2 flush time
Sample 2 integration
Sample 3 flush time
Sample 3 integration
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Two sample loops
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Two sample loops
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The Fast method
Additional software is used to control the ESI SC 4 DX FAST
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Smart use of the detector
The duty of cycle of an instrument can also effect the analysis times
Many instruments have optimized systems for different regions of thespectrum under analysis (mainly split in to UV and Vis)
The in order that these regions are read by the detector and how thedetector operates is know as the duty of cycle
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Traditional data acquisition for ICP
Traditional acquisition mode reads the wavelengths like this:
Vis replicate 1
UV replicate 1
Vis replicate 2
UV replicate 2
Vis replicate 3
UV replicate 3
Each time the ICP-OES switches view there is overhead time.
For a three replicate analysis there are 6 transitions
Therefore six lots of overhead time
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Speed mode for optimized data acquisition
Removal of the overhead time
UV replicate 1,2,3
One transition
Visible replicate 1,2,3
Allows for up to 30% more samples to be analysed
Traditional
Speed
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Data Acquisition Mode Sprint mode
Accessible on ALL iCAP 6500 models Uses the same sample replicate cycle as Speed mode
Reduced detector overhead time by use of CSPI
3 seconds per slit (for 0-20 wavelengths)
4 seconds per slit (for 20-75 wavelengths)
Typically achieves 3% RSDs on replicate measurements
Enables fast data acquisition when using both UV & Vis slits
High throughput wear metal applications
High throughput Argri/Enviro applications
High throughput Geochem screening
Enhanced data acquisition for high speed analysis
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How Cumulative Set Pattern Integration works
Each wavelength is read in order
If the counts are reaching the limit which the pixel can hold the countsare recorded and the pixel is rested and allowed to accumulate morecounts, if not the next wavelength is interrogated
High intensity wavelengths (high concentration) will cause pixels to fillup quickly
P lli i
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Polling question 2
Which of these is most important for your lab when thinking about
instruments? Instrument sensitivity
Speed of analysis
Operating costs of the instrument
Ease of use
P lli i 2 R l
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Polling question 2 Results
I l i f h h l i l b
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Implementation of the technology in your lab
Two applications both environmental
Agricultural trend analysis
Extremely high sample numbers (1000s of samples a day) High sensitivity not critical
An EPA analysis using the 6010C
Moderate sample numbers (100s of samples a day)
High sensitivity is key
Examples use The Thermo Scientific iCAP 6500 ICP-OES
EXI SC 4- DX FAST
E l 1 T d E i t l l i
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Example 1 - Trend Environmental analysis
Analysis of surface soil for major, trace and micro-nutrients from arable
land to determine fertiliser concentrations Analysis of foliage during the growing season to determine the
concentration of fertiliser to be applied.
Results of analysis are then mapped and the dose of fertiliser isautomatically changed as the farmer moves across the land
T d E i t l A l i
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Trend Environmental Analysis
Sensitivity and speed
Even 1s integration yields adequate detection limits for this type of
analysis Stability
Essential for long runs
Full wavelength coverage allows selection of appropriate wavelengthfor expected concentration
Matrix Tolerance
Solid State generator, swing frequency
Low cost of ownership
Th l ti il l
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The sample preparation- soil as an example
This type of analysis is not regulated but the accepted
method is
Sample is dried overnight and ground
~5g aliquot is placed in to a 30ml vial
20ml ammonium acetate of Mehlich 3 solution
Shaken Filtered
Analysed
P t
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Parameters
Parameter Setting
Pump speed 40rpm
Nebulizer gas flow 0.65 L/min
Spray Chamber Baffled mini cyclonic (25 ml)
Integration times UV/Vis 5 second per region
Number of replicates 1
Analysis mode Sprint
Loop volume 750l (total vol used 1.5ml)
Loop fill time 1 second
Total sample flush time 2.5 seconds
High nebulizer gas flow reduces flush time
Small spray chamber volume - reduces flush time and memory
Small loop volume minimal sample usage
S l l i
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Sample analysis
The iCAP 6500 ICP-OES wascalibrated
60 samples analyzed
Two different soils
Determine repeatability
Precision, accuracy
Blanks
To determine detection limits
Look at carry over after samples
A QC sample every ten samples
Element High Std concmg/L
Correlation
B 249.773 nm 5 0.994
Ca 227.547 nm 3000 0.999
Cu 244.700 nm 10 1.000
Fe 238.863 nm 100 0.992
K 769.800 nm 500 0.989
Mg 279.079 nm 300 0.995
Mn 293.306 nm 50 0.995
Na 818.326 nm 75 0.994
P 213.618 nm 100 0.999S 182.034 nm 50 1.000
Zn 206.200 nm 5 0.999
Res lts
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Results
66 samples analyzed in 15 minutes - 13.6 seconds a sample
Element Soil A mg/L Soil B mg/L QC Sample
Measured mg/L True mg/L Recovery %B 249.773 nm 1.21 1.15 2.65 2.5 105.9
Ca 227.547 nm 330 996 3238 3000 107.9
Cu 244.700 nm ND 0.88 10.2 10 102.4
Fe 238.863 nm 22.8 17.44 106 100 106.4
K 769.800 nm ND ND 493 500 98.6
Mg 279.079 nm 106 30.6 315 300 104.8
Mn 293.306 nm 1.60 13.9 53.3 50 106.5
Na 818.326 nm 11.8 16.9 81.4 75 108.6
P 213.618 nm 14.9 37.7 98.0 100 98.0
S 182.034 nm 15.7 9.35 49.2 50 98.3
Zn 206.200 nm 0.33 49.6 5.08 5 101.7
Example 2 US EPA Method 6010C
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Example 2 US EPA Method 6010C
Analysis of waters, soils and sludge following the
digestion and filtration of soils and sludge
Acidification of waters
This method and variations of this method are widely used in NorthAmerica and around the world.
Parameters
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Parameters
Parameter Setting
Pump speed 40rpm
Nebulizer gas flow 0.65 L/min
Spray Chamber Baffled mini cyclonic (25 ml)
Integration times UV/Vis 5 second per region
Number of replicates 3
Analysis mode Sprint
Loop volume 2000l (total vol used 3 ml)
Loop fill time 5 second
Total sample flush time 8 seconds
High nebulizer gas flow reduces flush time
Small spray chamber volume - reduces flush time and memory
Integration times longer before achieve the required sensitivity
Method
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Method
The iCAP 6500 ICP-OES (Duo) was used for the analysis
Axial view for UV region, Radial view for Visible region A Sc internal standard was used
Axial view with Sc 227.318 nm internal
std
Radial view with Sc 361.384 nm internal
stdAs 189.042 nm, Cd 226.502 nm,
Co 228.616 nm, Cr 205.552 nm,
Hg 194.227 nm, Mo 202.030 nm,
Ni 221.647 nm, P 177.495 nm,
Pb 220.353 nm, Sb 206.833 nm,Se 196.090 nm, Ti 190.856 nm,
Zn 213.856 nm
Ag 328.068 nm, Al 328.068 nm,
B 249.678 nm, Ba 493.409 nm,
Ca 315.887 nm, Cu 34.754 nm,
Fe 259.940 nm, K 766.490 nm,
Li 670.784 nm, Mg 279.553 nm,Na 588.995 nm, Si 251.611 nm,
Sr 407.771 nm, Ti 334.904 nm,
V 292.402 nm
Spectral inferences and optical stability
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Spectral inferences and optical stability
Previous work demonstrates the iCAP 6500 ICP-OES (duo) ability to
resolve the interferences mentioned in the 6010 method, with the use ofthe relevant interference check solutions
Application note 40836
Sample introduction parameters will not effect the spectral interferences
Linear range
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Linear range
As the mode of data
collection is different linearrange was investigates
Sprint mode uses CSPI
> 2 mg/L > 50 mg/L >500 mg/L
Hg 194.227 nmAg 328.068 nm
As 189.042 nmB 249.678 nm
Ba 493.409 nm
Cd 226.502 nm
Co 228.616 nm
Cr 205.552 nm
Cu 34.754 nm
Li 670.784 nm
Mg 279.553 nm
Mo 202.030 nm
Ni 221.647 nm
P 177.495 nm
Pb 220.353 nm
Sb 206.833 nm
Se 196.090 nm
Si 251.611 nmSr 407.771 nm
Ti 334.904 nm
Tl 190.856 nm
V 292.402 nm
Zn 213.856 nm
Al 328.068 nmCa 315.887 nm
Fe 259.940 nm
K 766.490 nm
Na 588.995 nm
Detection limits and Sample timings
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Detection limits and Sample timings
Analysis time per sample for the 6010method was less than 50 Seconds
Instrument detection limits compared toEPA estimates
Element DL ug/L EPA ug/L Element DL ug/L EPA ug/L
Ag 4 4.7 Mg 15 20
Al 27 30 Mo 2 5.3
As 12 35 Na 32 (19) 19
B 3 3.8 Ni 5 10
Ba 0.7 0.87 P 11 51
Ca 17 (7) 6.7 Pb 3 28
Cd 2 2.3 Sb 6 21
Co 1 4.7 Se 9 50
Cr 0.9 4.7 Si 12 17
Cu 3 3.6 Sr 0.3 0.28
Fe 9 (3) 4.1 Ti 4 5
Hg 3 17 Tl 7 27
K 60 - V 5 5
Li 7 2.8 Zn 1 1.2
Summary
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Summary
Simple optimization of sample introduction can reduce sample analysis
times for ICP-OES and ICP-MS Use of accessories such as single loop ESI SC FAST can reduce these
times further
For ICP-MS there is the added benefit of the cones seeing less matrixreducing user maintenance
Use of the ESI SC 4 DS FAST dual loop with the Thermo ScientificiCAP 6500 ICP-OES in Sprint mode can reduce sample introductiontimes significantly
Typically more than 2 minutes per sample to less than 50 seconds for aEPA method!
Question and Answer
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Question and Answer
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