gulf coast conference galveston, tx october 15-16, 2013 · 2016-09-03 · gulf coast conference...

Gulf Coast ConferenceGalveston, TX

October 15-16, 2013

Determination of metals in Petroleum and Energy Industry Matrices via Microwave Plasma Atomic Emission

Greg GillelandApplication Engineer, Atomic

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Abstract

Agilent 4100 MP-AES produces robust and stable nitrogenplasma using magnetically coupled microwave energy andprovides superior detection limits and extended working rangecompared to flame atomic absorption. A nitrogen gas generatorcan be used to feed the plasma and source lamps are notrequired, significantly reducing operating costs while improvinglaboratory safety by eliminating flammable and oxidizingcompressed gases. The design and operation of this newinstrument for elemental determinations will be discussed.Methods developed and results obtained for the multi-elementdetermination of metals in ethanol, diesel and oil samples willbe presented.

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Measurement challenge

ChallengeSimply and effectively determining elemental values -- includingsulfur and phosphorous -- in various organic matrices using theAgilent MP4100 Microwave Plasma Atomic EmissionSpectrometer.

SolutionThe Agilent 4100 MP-AES spectrometer allows quick, accurateand inexpensive multi-element analysis of organic matrices. Theexternal gas control module (EGCM) allows for a nitrogen purge ofthe monochromator, making it possible to run wavelengths<190nm easily and accurately.

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The Agilent 4100 MP-AES

A Revolutionary and Economical Solution for Elemental Analysis in Your Laboratory

Common Challenges facing Laboratories performing Elemental Analysis Today• Increased need for fast, multi-element determination over a wide

dynamic range in a wide array of matrices

• Desire to reduce the overall cost of analysis due to rising costs (instrument supplies and consumables – power, labor, etc)

• Difficulty in sourcing some gases – especially in remote areas

• Availability of suitably trained personnel to develop methods, perform sample measurements and interpret results

• Some laboratories under pressure to improve safety by removing flammable gases

Higher Performance

• Ideal flame AA alternative• Handles major, minor & most trace

levels• Matrix handling to match flame AA

Lower Cost of Ownership

• Runs on air• Multi-element unattended

operation• Moderate sample

throughput

Faster Measurement

& Easy Operation

• Fast sequential measurement• Simultaneous background

correction• New generation software• Plug & Play torch

Safer Laboratory Operation

• No flammable gases• Unattended multi-

element operation

Key Customer Benefits

How Does MP-AES Work?

• Nitrogen can be supplied either via bottled gas, liquid dewars or via an optional nitrogen generator

• Magnetic excitation gives a toroidal plasma and an effective central zone for sample injection

• The nitrogen plasma…– provides a robust, high temperature source in conventional

torches (approx. 5000 K).– provides a cooler central channel suitable for sample

atomization.– creates high intensity atomic emission lines with fewer

spectral interferences than ICP-OES.

How Does MP-AES Work?Agilent’s patented microwave waveguide technology

Simple, Foolproof Torch InstallationNo Alignment, No GuessworkThree Easy Steps!

Schematic Diagram of Agilent MP4100

1. Instrument exhaust2. Pre-optics window3. Torch loader4. Peristaltic pump5. Plasma enable button6. High voltage power supply7. Electronics (control PWB)8. Pre-optics9. Plasma (Magnetron)10. Monochromator with CCD detector11. External gas control module12. Cooling air inlet13. Inlet gas connections

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3 sigma DL’s using a 10 second integration time with dewar nitrogen

Element Flame AA

MP-AES

% Diff

K 0.8 0.65 -18.8

Ca 0.4 0.05 -87.5

Mg 0.3 0.12 -60.0

Na 0.3 0.12 -60.0

Au 5 1.8 -64.0

Pt 76 4.5 -94.0

Pd 15 3.8 -74.7

Ag 1.7 0.5 -70.6

Rh 4 0.5 -87.5

DL’s in ppb, aqueous samples

Performance Comparison vs. Flame AA– Typical Detection Limits

Element Flame AA

MP-AES

% Diff

As* 60 45 -25.0

Cd 1.5 1.4 -6.7

Cr 5 0.5 -90.0

Mn 1.0 0.25 -75.0

Pb 14 4.4 -68.6

Sb 37 12 -67.6

Se* 500 70 -86.0

Zn 1.6 2.8 +75.0

* 30 second integration time used for As and Se

Wide Dynamic Range

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10

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1 10 100 1000 10000

Cer

tifie

d (m

g/kg

)

Measured (mg/kg)

Phosphorus (r=1.0000)

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1000

10000

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1 10 100 1000 10000 100000

Cer

tifie

d (m

g/kg

)

Measured (mg/kg)

Potassium (r=0.9999)

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1 10 100 1000 10000

Cer

tifie

d (m

g/kg

)

Measured (mg/kg)

Magnesium (r=0.9997)

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tifie

d (m

g/kg

)

Measured (mg/kg)

Calcium (r=1.0000)

Chemical and Petrochemical Applications

Additives in Lubricating Oil

Metals in Calcined Coke

Metals in Gasoline and

Biodiesel

Metals in Polymers

Organic Applications – The Challenge

• Plasma instability• May extinguish the plasma

High vapour pressure from solvents

• Poor precision and drift• Down time - injector may require regular

cleaning

Carbon build up in injector

• Poor precision• Down time - nebulizer needs cleaningNebulizer blockage

Organics Kit – Inert OneNeb Nebulizer

• Robust PFA and PEEK construction– Inert - resistant to strong acids such as HF– Resistant to breakage

• Moulded plastic design provides improved nebulizer to nebulizer reproducibility

• Constant diameter narrow bore tubing through to nebulizer tip– Ideal for high solids/particulates– Improved tolerance to high TDS samples

• Narrow aerosol size distribution provides improved precision

• Compatible with a wide flow range from0.1 to 2 mL/min.– No sensitivity loss at low flow rates

Organics Kit - External Gas Control Module (EGCM)

• Air injection prevents carbon build up on the injector when running organics

• Reduces the background emissions from organics present in the plasma

• A controlled flow of air is bled into the Auxiliary gas flow through the torch

• Nitrogen purge option allows analysis of wavelengths <190nm

Solvent Background can be Minimized with EGCM

Organics – Long Term Stability

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0:00 1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00

Norm

alize

d Con

c

Time (h:mm)

Zn 213.857 nm Si 251.611 nm Fe 259.940 nm Ni 305.081 nm

Ag 328.068 nm Pb 283.305 nm Cu 327.395 nm Mg 285.213 nm

Ti 334.941 nm Al 396.152 nm

10 ppm S21. Precision of <<1% RSD for all lines.

Sample PreparationMilestone UltraWave Microwave Digestion Unit

0.25g sample1mL H2O4mL HNO3QS to 50mL

October 21, 2013Confidentiality Label

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MP4100 Instrument ParametersSRM Analysis

Parameter SettingNebulizer Inert OneNebSpray chamber Double-pass glass cyclonicSample tubing White/whiteWaste tubing Blue/blueRead Time 3 sReplicates 3Stabilization time 15 sFast Pump (80 rpm) OnBackground correction AutoPump speed 10 rpm

MP4100 - Measured Results for NIST SRM 1848 Lubricating Oil Additive Package

Element Certified Value, mg/kg

Average MP4100 Result, mg/kg SD % Recovery

B 1370 1417 84 103.4%Ca 3590 3342 353 93.1%Mg 8210 7566 191 92.2%P 7880 6994 1010 88.8%S 23270 19442 1539 83.5%Zn 8730 7810 1038 89.5%

MP4100 - Measured Results for Conostan S-21 standard


Average MP4100

Result, mg/kg% Recovery

Fe 10 10.8 107.9%Mg 10 10.5 105.2%Ni 10 10.4 104.1%P 10 10.6 106.4%Zn 10 9.3 92.6%

MP4100 - Measured Results for NIST SRM2719Calcined Petroleum Coke


Average MP4100

Result, mg/kgSD % Recovery

Al 58.9 58.8 2.0 99.9%Ca 57.7 49.5 5.5 85.8%Fe 201.6 166.6 20.0 82.6%V 58.6 50.7 4.1 86.4%

MP4100 - Measured Results for NIST SRM2719Calcined Petroleum Coke

ElementSample

Measured, ppm

SpikeMeasured,

ppmSpike % Recovery

Al 0.94 1.95 1.00 101%Ca 0.30 1.21 1.00 91.0%Fe 0.72 1.77 1.00 105%Ni 0.56 1.54 1.00 97.8%S 25.3 34.5 10.0 92.0%V 0.17 1.12 1.00 95.0%

MP4100 Analysis of BioDiesel FuelSample Preparation – Method EN14538A commercial diesel sample was analyzed

• 1:10 dilution with Shellsol

Standards made from Conostan S21+K

• 0.5 ppm, 1 ppm, 5 ppm, 10 ppm

All samples and standards matrix matched with blank oil

MP4100 Instrument ParametersBioDiesel Fuels

Parameter SettingNebulizer Inert OneNebSpray chamber Double-pass glass cyclonicSample tubing Orange/green solvent resistantWaste tubing Blue/blue solvent resistantRead Time 3 sReplicates 3Stabilization time 15 sFast Pump (80 rpm) OnBackground correction AutoPump speed 5 rpm

Method Detection LimitsBioDiesel Fuels3σ, 3s read time, 10 blanks

Element Wavelength (nm)

MDL (ppb)

Mg 285.213 2.7Ca 422.673 8.2Na 588.995 18.7K 766.491 2.7

Spike RecoveriesBioDiesel FuelsDiesel fuel sample spiked with 0.55 ppm S21+K

Element Sample (ppm) Spiked Sample(ppm)

Recovery (%)

Mg 285.213 nm < MDL 0.53 97Ca 422.673 nm < MDL 0.51 93Na 588.995 nm < MDL 0.51 93K 766.491 nm < MDL 0.51 93

New Generation MP Expert Software

Agilent Confidential



• Windows 7 optimized, worksheet based software

• Fresh, clean and intuitive look and feel

• Powerful Method-Development Tools

• Provides capability for applet-style operation using preset methods, or access to full capabilities

• Automated optimization tools

New Generation MP Expert SoftwareWorksheet-Based Architecture


New Generation MP Expert SoftwareIntuitive, Easy to Navigate


New Generation MP Expert SoftwareMethod Development



• Select Elements from Periodic Table or Alphabetically from Dropdown Menu

• Default Wavelength Generally has Highest Signal/Background

• Alternate Wavelengths are Available From Dropdown Menu



• Spectral Neighbourhood is Represented in Tabular Form

• Operator is Able to Sort Out Likely Interferents Based on Spectral Proximity and Relative intensity



• Spectral Region is also Shown in Graphic Form as a Plot of Relative Intensity vs. Wavelength


New Generation MP Expert SoftwareApplet-Style Operation


New Generation MP Expert SoftwareApplet-Style Operation


• Very Easy to Use, No Guesswork• Especially Well-suited to Labs With Multiple Operators/Shifts• More Qualified Analysts Maintain Access to Method Development Tools

New Generation MP Expert Software Optimization Tools


Accessory Options for the 4100 MP-AES• Automate and simplify analysis with the SPS3 autosampler

(required for unattended overnight operation)

• For organic applications, use the EGCM to bleed air into the plasma minimizing carbon build-up and reducing background– also requires the OneNeb inert nebulizer (included with the

Organics kit)

• For low ppb level detection of As, Se or Hg, use the Multimode Sample Introduction System (MSIS)– also requires the 5 channel peristaltic pump option

Typical DLs for MSIS:

As 1.0 mg/L Se 2.0 mg/L Hg 0.5 mg/L

Runs on air – the most significant advance in atomic spectroscopy

o Lowest running cost of any atomic spectroscopy technique due tocapability to run on air – ideal for remote and at site operation

o Improved safety – capability to run on air means no flammable gasesand no manual handling of cylinders

o Easy-to-use software with MP applets and plug and play torch whichsimplify operation and maximize uptime

oSuperior performance to flame AA, with capability to run unattended overnight

Agilent 4100 MP-AES

50 ASTS 2012

gulf coast conference galveston, tx october 15-16, 2013 · 2016-09-03 · gulf coast conference...

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