The Determination of Target Elements in Oil and Aqueous … · 2016. 9. 4. · October 29, 2014...

The Determination of Target Elements in Oil and Aqueous Matrices Utilizing the Agilent 4200 Microwave Plasma - Atomic Emission Spectroscopy (MP-AES)

Presenter: Christine Rivera, Agilent Technologies

Agilent’s Atomic Spectroscopy Portfolio

October 29, 2014

Confidentiality Label

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Early Research in Microwave Plasma • 1976 – review of MP of research by Skogerboe and Coleman.

• Analytical Chemistry, Vol 48. No. 7, June 1976 - CMP – capacitively coupled microwave plasma (requires conductive

electrode) - MIP – Microwave induced plasma (electrodeless)

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Early research conclusion

• CMP was better suited for elemental analysis • Sample is introduced from peripheral boundary of the plasma. This lead

to analytical problems.

• MIP was better suited as an atomization/ionization source for GC

• Could not handle lots of liquid as the plasma would extinguish.

• CONCLUSION: “Plasmas produced with low power microwave supplies show considerable promise as spectral excitation sources.”

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MIPS

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MP-AES technology research at Agilent • CMP and MIP systems not adequate for routine elemental

spectroscopy - needs new approach.

• Used axial magnetic and radial electric field from microwave source to sustain plasma.

Senior Research Engineer: Michael Hammer

Senior Development Engineer: Hugh Stevenson

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Award winning MP-AES

2013 AIRG medal

2012 R&D 100

Neon Pink plasma is BORN!

MP-AES Microwave Plasma – Atomic Emission Spectrometer • A multi element atomic

spectroscopy instrument.

• Wide application reach.

Chemical and Petrochemical

Mining and

Geochemical

Food and Agriculture

Environmental

Pharmaceutical

Academia

Schematic Diagram 1. Instrument exhaust 2. Pre-optics window 3. Torch loader 4. Peristaltic pump 5. Plasma enable button 6. High voltage power supply 7. Electronics (control PWB) 8. Pre-optics 9. Plasma (Magnetron) 10. Monochromator with CCD detector 11. External gas control module 12. Cooling air inlet 13. Inlet gas connections

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

• Using nitrogen as the plasma gas gives a robust plasma with a conventional torch. Nitrogen is supplied either via Agilent 4107 N2 generator

• Magnetic excitation gives a toroidal plasma and an effective central zone for sample injection (axial magnetic fields and radial electrical fields)

• The microwave magnetically excited nitrogen plasma - Provides a robust, high temperature source in conventional torches

(approx. 5000 K) - A defined central channel suitable for sample introduction and atomization - Creates high intensity emission lines

Microwave Plasma Emission Overview

Ground State Excited State Emission

Monochromator & Detector

Quantitation

Atomization

Optical Diagram

4200 Easy Fit Torch

Monochromator

Pre-optics Detector

Higher Performance

• Ideal flame AA alternative

• Handles major, minor & most trace levels

• Wider linear dynamic range • Lower detection limits

Easy Operation

• New generation software • Simultaneous auto background correction • Plug & Play torch

Safer Laboratory Operation

• No flammable gases • Unattended multi-element

operation

Key benefits of MP-AES

Lowest cost of ownership

• Runs on air! • Eliminates on-going gas

supply costs

Emission Spectra

The N2 MP-AES ...

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300 nm

High intensity atomization lines for Mo

ICP-OES

MP-AES

Simpler atomization emission spectra suitable for atomic spectroscopy

Agilent 4200 MP-AES

Mass flow control of nebulizer gas and robust sample introduction: Enhanced accuracy and long term stability in tough samples.

Optimized, second generation plasma system and new torch design: Expanding the application range to include a broad range of complex matrix samples.

MP Expert v1.4: Intuitive software interface, now with advanced features in the ‘PRO’ pack.

4200 Expanded Application Range

• Design changes to the self aligning Easy Fit torch, combined with optimized waveguide enables a broader range of samples to be analyzed.

• Digest solutions with up to 3% TDS are capable of being analyzed

• Food and Agriculture, Geochem, petrochem, and environmental.

Demonstration of system robustness

Plasma OFF Plasma ON

Plasma STILL ON Plasma STILL ON

Demonstration of System Robustness

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ASTS 2014 - San Francisco

Application Examples

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Still the leader in Xenon flash lamp technology after 12 years!

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Applications MP-AES Can Do – by Market

Determination of Elements in Viscous Oil and Reclamation Water Utilizing the 4200 MP-AES

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Introduction The ability to monitor the amount of residual target elements in reclaimed used oil is a necessity for the reclamation process. The number of elements and the respective action levels are dependent of the use of the reclaimed and cleaned oil.

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Agilent Confidential

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Test Articles Sample Preparation Final Dilution Comments

Viscous Oil # 1 0.5723 gms 30 gms PremiSolv™

Heated (25oC) and sonicated until complete dissolution Viscous Oil # 2 0.5973 gms

Reclamation water

Sample was filtered using a 0.45 µm filter. The filtrate was transferred to a centrifuge tube and spun until clear. The clear solution was decanted into a separate single-use tube for analysis.

Neat

Serial Dilution of 5X, 2 mL of water diluted to 10 mL with 1% nitric acid

Target Elements Al Fe Mn

Ca K Na

Cr Mg Ni

Objectives 1. Ability to run both oil and aqueous samples

The oil and water samples were analyzed on the 4200 MP-AES in two separate methods. The oil samples were dissolved in Premasolv®, which is a low odor kerosene replacement solvent. Once the PremiSolv™ analysis sequence was completed, the solvent was rinsed from the sample introduction system (SIS) with ethanol and then water. The water analysis was performed. The time to switch over to the aqueous solvent was approximately 15 minutes.

2. Method Detection Limits The instrument detection limit (IDL) and the method detection limit (MDL) were calculated utilizing organic and aqueous 0.050 ppm standards. The MDL is represented as the IDL corrected for the sample preparation dilution factor.

3. Results The accuracy of the method for the oil matrix was assessed by spiking the oil samples with a known concentration of the target analytes. A %recovery was calculated for each element in the oil sample. The accuracy of the method for the water (slurry) sample matrix was assessed by performing a serial dilution and comparing the results determined in the neat solution to those in the dilution. The precision of the method were assessed by analyzing the test solutions in triplicate The water sample was not spiked but a serial dilution was performed to assess the accuracy of the result by minimizing the matrix.

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MP-AES Configuration

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Easy as 1, 2, 3….. The torch assembly is single action for automatic gas connection and reproducible positioning analyst to analyst.

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Next, Install the spraychamber with the easy fit clamp and connect the pump tubes

Agilent – OneNeb Nebulizer

The capillary tubing extends nearly to the tip. The geometry at the tip is carefully dimensioned to allow the carrier gas (argon or nitrogen) to mix with the sample liquid. The result is an aerosol consisting of droplets with a narrow size-distribution range.

Characteristics: Robust PFA and PEEK construction

- Inert - resistant to strong acids such as HF

- Resistant to breakage - Molded 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 • Handles a wide flow range from 0.1 to

2 mL/min. - No sensitivity loss at low flow rates

Ease of Use - MP-AES verses FAAS • Simple sample preparation

- Reduced chemical and ionization interferences minimizes need for addition of extra reagents

• Lower costs, higher sample throughput • Reduces introduction of possible contaminants

Element Possible Chemical Interference FAAS specific sample preparation MP-AES specific sample preparation

Al

Ionization effects Potassium nitrate

None Enhancement due to presence of specific elements*

optimize burner height and carefully adjust fuel/oxidant ratio

Refractory compound Lanthanum releasing agent

Ca Refractory compound Lanthanum releasing agent

None Ionization effects Cesium ionization buffer

Cr Depressed Signal nitrous-oxide flame or careful optimization of fuel/oxidant ratio None

Fe None None None

K Ionization effects Cesium ionization buffer None

Mg Refractory compound Lanthanum releasing agent None

Mn None None None

Na Ionization effects Cesium ionization buffer None

Ni None None None

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Target Elements Al Fe Mn

Ca K Na

Cr Mg Ni

MP-AES Performance Working concentration range

Optimum working range comparison between FAAS and MP-AES

Element 4200 MP-AES,

mg/L Linear correlation

coeft MP-AES FAAS, mg/L

Ca 422.6 0-20 0.9999 0.01-10 Mg 518.3 0-100 0.99988 0.15-20 (202.6) Na 589.5 0-20 0.99996 0.01-2 K 769.9 0-100 0.99968 1-6

Example: K 769.9nm calibration for 4200 MP-AES

Method Parameters PremiSolv™ Solvent Diluent Conditions

Aqueous Diluent Conditions

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Auto-Optimization Tool

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Ease of Use

Simple software • Auto optimization tools

• Auto Background Correction

• Applet quick start methods

Intuitive Software

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Method Detection Limit (ppm) PremiSolv™ Solvent – 0.025 ppm Solution

Solution Label

Al 396.152 nm

Ca 393.366 nm

Cr 425.433 nm

Fe 438.354 nm

Mg 285.213 nm

Mn 403.076 nm

Ni 341.476 nm

0.025_1 0.028 0.026 0.027 0.031 0.029 0.028 0.033 0.025_2 0.027 0.026 0.026 0.029 0.028 0.027 0.033 0.025_3 0.028 0.026 0.026 0.028 0.027 0.027 0.030 0.025_4 0.028 0.025 0.026 0.026 0.028 0.027 0.029 0.025_5 0.028 0.025 0.026 0.027 0.027 0.026 0.028 0.025_6 0.028 0.025 0.026 0.026 0.027 0.026 0.027 0.025_7 0.028 0.025 0.026 0.025 0.027 0.025 0.026 0.025_8 0.027 0.025 0.026 0.026 0.027 0.025 0.025 0.025_9 0.027 0.025 0.026 0.027 0.027 0.024 0.022

0.025_10 0.027 0.025 0.027 0.026 0.027 0.024 0.023 Ave 0.027 0.025 0.026 0.027 0.028 0.026 0.027 SD 0.00047 0.00046 0.00027 0.00164 0.00047 0.00150 0.00362

%RSD 1.7 1.8 1.0 6.0 1.7 5.8 13.2 %REC 105 97 100 104 105 98 105

IDL 0.0013 0.0013 0.0008 0.0047 0.0013 0.0043 0.0103 MDL 0.067 0.066 0.039 0.23 0.067 0.21 0.52

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Due to inherent high response for Na and K in the reagent blank, the IDL and MDL could not be determined/calculated in this manner. As a result, the low standard concentration was used for the IDL The low standard concentration for K was 0.50 ppm and Na was 0.10 ppm.

Viscous Oil Sample # 1 PremiSolv™ Accuracy and Precision

Solution Label

Al 396.152

nm

Ca 393.366

nm

Cr 425.433

nm

Fe 438.354

nm

K 769.897

nm

Mg 285.213

nm

Mn 403.076

nm

Na 589.592

nm

Ni 341.476

nm Viscous oil #1_1 < MDL 0.98 0.0071 2.5 0.27 0.042 < MDL 4.0 0.94 Viscous oil #1_2 < MDL 1.1 0.0079 2.7 0.30 0.049 < MDL 4.4 1.1 Viscous oil #1_3 < MDL 1.2 0.0086 2.8 0.32 0.051 < MDL 4.5 1.1

Average 1.1 0.0079 2.7 0.30 0.047 4.3 1.0 %RSD 9.0 9.5 4.9 7.8 9.3 6.1 8.4

#1_spk _1 3.1 4.7 3.1 5.2 3.3 3.2 2.9 8.1 4.1 #1_spk _2 3.1 4.5 3.1 5.2 3.3 3.2 2.8 8.3 4.1 #1_spk _3 3.1 4.5 3.2 5.3 3.4 3.2 2.9 8.5 4.1

Average 3.10 4.6 3.15 5.3 3.3 3.2 2.9 8.3 4.1 %RSD 0.23 3.3 0.71 1.1 0.97 0.56 0.61 2.0 0.22 %REC 103 116 105 86 101 104 95 134 101

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3 ppm spike amount

Viscous Oil Sample # 2 PremiSolv™ Accuracy and Precision

Solution Label

Al 396.152

nm

Ca 393.366

nm

Cr 425.433

nm

Fe 438.354

nm

K 769.897

nm

Mg 285.213

nm

Mn 403.076

nm

Na 589.592

nm

Ni 341.476

nm Viscous Oil #2_1 < MDL 0.014 0.020 3.2 0.29 0.0057 < MDL 0.28 1.4 Viscous Oil #2_2 < MDL 0.013 0.019 3.2 0.29 0.0061 < MDL 0.29 1.4 Viscous Oil #2_3 < MDL 0.013 0.016 3.0 0.28 0.0079 < MDL 0.28 1.3

Average 0.01 0.02 3.1 0.28 0.007 0.29 1.4 %RSD 5.9 12 3.1 1.7 18 2.3 3.8

#2_spk _1 1.6 1.6 1.7 4.3 1.8 1.6 1.5 1.9 2.8 #2_spk_2 1.7 1.7 1.7 4.3 1.7 1.7 1.5 1.9 2.9 #2_spk_3 1.7 1.7 1.7 4.4 1.7 1.8 1.5 1.9 2.9

Average 1.7 1.7 1.7 4.3 1.7 1.7 1.5 1.9 2.9 %RSD 1.6 2.9 0.8 1.1 1.4 5.7 1.7 0.2 2.1 %REC 103 104 105 75 90 105 94 101 92

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1.6 ppm spike amount

Final Results – Viscous Oil Samples mg/kg

Solution Label Al

396.152 nm

Ca 393.366

nm

Cr 425.433

nm

Fe 438.354

nm

K 769.897

nm

Mg 285.213

nm

Mn 403.076

nm

Na 589.592

nm

Ni 341.476

nm Viscous oil #1_1 < MDL 52 0.38 130 340 2.2 < MDL 220 50 Viscous oil #1_2 < MDL 61 0.42 140 390 2.6 < MDL 240 57 Viscous oil #1_3 < MDL 62 0.46 150 420 2.7 < MDL 250 59

Average < MDL 58 0.42 140 380 2.5 < MDL 240 56

Viscous Oil #2_1 < MDL 0.72 1.0 160 620 0.28 < MDL 3.2 71 Viscous Oil #2_2 < MDL 0.66 1.0 160 620 0.30 < MDL 4.1 72 Viscous Oil #2_3 < MDL 0.65 0.83 150 490 0.40 < MDL 5.5 67

Average < MDL 0.67 0.94 160 580 0.33 < MDL 4.3 70

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Method Detection Limit (ppm) Aqueous – 0.050 ppm Solution

Solution Label

Al 396.152

nm

Ca 393.366

nm

Cr 425.433

nm

Fe 438.354

nm

K 769.897

nm

Mg 285.213

nm

Mn 403.076

nm

Ni 341.476

nm 0.050_1 0.047 0.049 0.044 0.046 0.048 0.054 0.051 0.052 0.050_2 0.045 0.049 0.046 0.049 0.050 0.051 0.053 0.056 0.050_3 0.044 0.049 0.047 0.050 0.048 0.051 0.050 0.055 0.050_4 0.046 0.049 0.046 0.050 0.047 0.051 0.051 0.053 0.050_5 0.046 0.048 0.046 0.049 0.046 0.050 0.052 0.055 0.050_6 0.044 0.048 0.046 0.049 0.045 0.051 0.050 0.052 0.050_7 0.044 0.049 0.046 0.049 0.046 0.050 0.050 0.050 0.050_8 0.045 0.048 0.047 0.048 0.046 0.050 0.050 0.050 0.050_9 0.045 0.049 0.045 0.050 0.044 0.051 0.050 0.050

0.050_10 0.045 0.049 0.046 0.048 0.045 0.050 0.051 0.051 Ave 0.045 0.049 0.046 0.049 0.046 0.051 0.051 0.052 SD 0.00095 0.00052 0.00081 0.0014 0.0016 0.0014 0.0011 0.0021

%RSD 2.1 1.1 1.8 2.9 3.5 2.7 2.1 4.0 %REC 90 97 92 98 93 102 102 105

MDL 0.003 0.002 0.003 0.004 0.005 0.004 0.003 0.007

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Aqueous Calibration Curve (Mg/L) Multi-Cal – Eliminates the Need for Dilution

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Element and Wavelength

(nm) Blank Standard

1 Standard

2 Standard

3 Standard

4 Standard

5 Standard

6 Al 396.152 0 0.05 0.1 0.5 5 20 Ca 393.366 0 0.05 0.1 0.5 5 -- Ca 422.673 0 -- -- -- 5 20 Cr 425.433 0 0.05 0.1 0.5 5 20 Fe 438.354 0 0.05 0.1 0.5 5 20 K 769.897 0 0.05 0.1 0.5 5 20

Mg 285.213 0 0.05 0.1 0.5 5 -- Mn 403.076 0 0.05 0.1 0.5 5 20 Na 589.592 0 -- -- 0.5 5 20 Na 330.237 0 -- -- -- -- 20 100 Ni 341.476 0 0.05 0.1 0.5 5 --

Multi-Calibration Example for Calcium

Ca 393.366 nm Ca 422.673 nm

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Final Results – Aqueous Samples mg/L

Solution Label

Al 396.152

Ca 393.366

Ca 422.673

Cr 425.433

Fe 438.354

K 769.897

Mg 285.213

Mn 403.076

Na 589.592

Na 330.237

Sample #1_1 17 Over 25 0.024 0.19 9.3 5.7 0.086 Over 120 Sample #1_2 18 Over 24 0.025 0.19 9.4 5.6 0.088 Over 120 Sample #1_3 18 Over 24 0.025 0.19 9.5 5.6 0.088 Over 120

Average 18 24 0 0 9 5.6 0.087 120 %RSD 1.5 1.2 2.0 1.0 1.0 0.9 1.7 0.0 Sample

#1_5X_1 17 19 0.027 0.18 9.1 5.7 0.10 Over 91 Sample

#1_5X_2 17 19 0.026 0.18 9.0 5.7 0.10 Over 90 Sample

#1_5X_3 17 19 0.026 0.18 8.9 5.7 0.10 Over 88 Average 17 19 0.026 0.18 9.000 5.7 0.10 90 %RSD 0.85 0.68 3.2 0.5 0.8 0.6 1.4 1.9

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Conclusions The 4200 MP-AES is the second generation of proven MP-AES technology

MP-AES offers safe, cost effective elemental analysis that is easy to use and offers excellent performance.

MP-AES can be used across a wide variety application types including aqueous and organic solvents

- Proven accuracy and precision - Cross calibration of primary and secondary wavelengths eliminates

excessive sample handling

Switch over from aqueous to organic solvents can be facilitated by purchasing a SIS for water and a SIS for organic

• Aspiration of a bridge solvent can convert from one matrix to another

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