PresentatioAchieving Ultra Fast, Low Cost Elemental Analysis

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


Sample 1 flush time

Sample 1 integration

Sample 1 loaded on to loop

Sample 1 injected to nebulizer

Autosampler moves to wash








Sample 2 flush time


Sample 3 flush time



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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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