AA Troubleshooting and Maintenance

Guidelines for Troubleshooting and Maintenance of AA Systems
Eric Vanclay Spectroscopy Consumables Product Manager Agilent Technologies, Inc. April 18, 2012
AA Maintenance & Trouble Shooting Apr. 2012
Todays Agilent: Atomic Spectroscopy

Worlds best, most complete atomic spectroscopy portfolio!
ICP-OES MP-AES ICP-MS
Flame AAS
Graphite Furnace AAS
AAS instruments can be flame only, furnace only, or combined (switchable)
Agilents Atomic Spectroscopy Portfolio - Features

Flame AA MP-AES Furnace AA ICP-OES ICP-MS
Lowest price
Single element DLs typically ~100s ppb Fast (for 1 element) Good elemental coverage Low running cost
Lowest running cost

Multi element DLs typically single to 10s ppb Faster Broader elemental coverage Lowest running cost
Trace levels at lowest price

Single element DLs typically 10s to 100s ppt Very slow Limited elemental coverage Moderate running cost
Fastest measurement
Multi element DLs typically single ppb Very fast Can measure most elements High running cost
Broadest coverage
Multi element DLs typically single or sub-ppt Fast Can measure almost all elements Highest running cost
Lowest
Selling Price
Highest
Common AA Problems Reported by Customers

Sensitivity:
Sensitivity is worse than it used to be I have a new application and I cant get the sensitivity I need How come I cant get the instrument to meet published detection limits?
Precision
Sensitivity is acceptable but precision is terrible
Accuracy
Instrument does not give the right results.
Poor Sample Throughput

The instrument throughput needs to improve Burner blocks too quickly
AA Sensitivity - What Impacts This?

4 areas of the instrument can affect sensitivity:
Sample introduction system (and AA lamp optimization) Method parameters Cleanliness Quality of standards used for calibration
Remember SMCQ Or System Must Create Quality
Sensitivity Quality of Standards

What concentration are they?
Low concentration standards have a finite life
Prepare ppb (ug/L) concentration standards daily from high conc. stock
Prepare low ppm (mg/L) concentration standards weekly
How are they prepared?

Ensure purchased standards are within Use By date Use calibrated pipettes and class A volumetric flasks for dilutions Use de-ionized water (Type I - conductivity > 18 M/cm3) lower grades may have contamination
How are they stored?

Plastic vessels ensure better stability
Stabilize with acid low pH ensures better stability

6 AA Maintenance & Trouble Shooting Apr. 2012
AA Sensitivity Sample Introduction

What to Check?
Lamp type and alignment
Alignment should be checked gain setting should be consistent
Lamp type can improve performance e.g. using high intensity UltrAA lamp
Optimum viewing height for Ca
Burner
Burner position must be optimized (vertical, horizontal & rotational positioning) Burner type changes path length (for air/acetylene elements)
AA Sensitivity Compromise
Ca N20/C2H2 Air/C2H2
Higher Sensitivity
Lower Noise
AA Sensitivity Sample Introduction

What to Check?
Nebulizer settings
Nebulizer uptake rate low flow rates better for high %TDS samples
Effect of impact bead position for absorbance signal with 5 ppm Cu
Impact bead position

Acetylene cylinder contents remaining (acetone can mask any signal)
AA Sensitivity Method Parameters

What to Check?
Gas flows
Flame stoichiometry affects sensitivity (oxidizing vs reducing flame)
Wavelength/Slit selection and Lamp current

Using the most sensitive line? Check youre using the rec. lamp current and slit width (different for multielement lamps)
Interferences?
Physical interferences can affect aerosol formation Use matched standards or standard additions Chemical interferences can reduce atom formation Use high temperature N2O/acetylene flame + appropriate matrix modifiers
Nitrous Oxide/Acetylene Flame Stoichiometry
Lean
Stoichiometric
Rich
11
AA Sensitivity System Cleanliness

What to Check?
Clean windows?
Check lamp and sample compartment windows Smudges or chemical residue reduces light throughput and increases noise
Sample Introduction System

Deposits in nebulizer can reduce sample uptake rate Solid material on burner slot reduces path length and increases noise Contamination in spray chamber impacts on aerosol formation increases noise
12
AA Sensitivity Rec. Settings

For most flame AA applications:
Fit the mixing paddles Optimize the impact bead for best sensitivity Use narrow bore capillary tubing
For highest flame AA sensitivity:

Remove mixing paddles
Adjust impact bead further away from the nebulizer Use wide bore capillary tubing (highest uptake rate)
For high TDS samples:

Fit the mixing paddles Adjust impact bead to 1 turn clockwise (towards nebulizer) from optimum sensitivity position
Use wide bore capillary tubing (to reduce chance of blockage)

Agilent Flame AA Performance Benefits

Flexibility, Ease of Use & Superior Flame Performance
Tunable performance means

Highest flame sensitivity: > 0.9 Abs. for 5 mg/L Cu
Best precision: < 0.5 % RSD using 10 x 5 s readings

Extended operation with difficult samples No loose gas hoses and no tools required for gas connection
Fast change-over to furnace operation (manual - < 30 s)
14
GFAA Sensitivity Sample Introduction

What to Check?
Lamp type and alignment
Alignment should be checked gain setting should be consistent Lamp type can improve performance e.g. using high intensity UltrAA lamp
Furnace workhead
Workhead position must be optimized (want light beam to pass through centre of graphite tube) Align lamp first (no workhead), then place workhead in position and align Light Beam Aligned Through Center of Graphite Tube
15
GFAA Sensitivity Sample Introduction

What to Check?
Sample Dispenser settings
Carefully adjust injection depth easy with the furnace camera
Autosampler rinse
Acidify rinse with 0.01 % (v/v) HNO3 plus a few drops of Triton X-100
Choice of inert gas impacts sensitivity

Argon gas preferred ensures optimum sensitivity and best tube life
Nitrogen gas reduces sensitivity by up to 20 % and decreases tube life
16
GFAA Sensitivity Correct Capillary Alignment

Correct dispensing Capillary tip must remain in contact with solution during dispensing Reduce dispensing height if sample spreads due to low surface tension Ensure there is no liquid on the outside of the capillary after dispensing
Pipet tip too high!
Pipet tip too low!
Ensure there is no liquid inside the capillary tip after dispensing
Sample should remain as a drop in the centre of the tube
GFAA Sensitivity Method Parameters

What to Check?
Furnace parameters
Set appropriate drying temperature and time (2-3 sec/uL of solution injected) Optimize ashing temperature using ashing study use SRM optimization
Ensure inner gas flow off just prior to atomization

Does the sample sizzle or splatter during the dry stage? Listen for the sound Use the mirror or furnace video to monitor the sample drying
18
Automated Furnace Method Optimization

SRM Wizard automates furnace optimization Optimizes absorbance as a function of ashing and atomization temperature Automatically creates a method using recommended conditions Reduces training requirements for new users
Optimization results for Pb determination using phosphate modifier
GFAA Sensitivity Method Parameters

What to Check?
Wavelength/Slit selection and Lamp current
Using the most sensitive line? Check youre using the rec. lamp current and slit width (different for multi-element lamps)
Interferences?
Physical interferences can affect sample spreading in the tube Maintain constant volume; use matched standards and partitioned tube Chemical interferences can reduce atom formation Use modifiers with temp. programming, matrix match & standard additions
20
GFAA Sensitivity Cleanliness

What to Check?
Clean windows?
Check lamp and sample compartment windows Smudges or chemical residue reduces light throughput and increases noise
Sample Introduction System

Deposits on capillary tip can affect sample dispensing Ensure no bubbles in dispensing syringe (current design is bubble free) Residues in graphite tube impacts on sensitivity may cause contamination, high noise or high background Condition tube before use (even if starting with a new tube) Helps to bed the tube in
21
Agilent Furnace AA Performance Benefits

Flexibility & Superior Furnace Performance
Competitor
Highest furnace sensitivity Best correction capability: < 2 % error at > 2 Abs. bground High speed correction Best capability to handle difficult samples
Agilent = More sensitivity Lower noise
22
Hydride AA Sensitivity Sample Introduction

What to Check?
Sample and reductant pump rates
Check the pressure bar - only apply enough pressure to ensure uniform flow Check pumping rates
Quartz cell positioning

Quartz cell position must be optimized (want light beam to pass through centre of the cell) Align lamp first (no cell), then place the cell into position and align Light Beam Aligned Through Center of Quartz Cell
23

What to Check?
Was the cell conditioned before use?
If required, recondition the cell again
Allow longer pre-read delay time (Hg needs a longer time)

Use an acid rinse between solutions Check acid tubing for deterioration Check/clean absorption cell
24

Low Signal with As: Check AsIII stable not being oxidized back to AsV Low Signal with Se:
Ensure KI not added before analysis

Low Signal with Hg:
Check that Hg is stabilized in solution

Avoid presence of KI clean system thoroughly with 1% sodium thiosulfate (or swap reagent modules)
25
Agilent Hydride AA Performance Benefits

Faster than graphite furnace technique 50 70 analyses per hour Relative easy to automate Analyte is removed from matrix Eliminating matrix interferences Minimizing background Can easily analyze matrices that are difficult to run by graphite furnace 100 % sampling efficiency Detection limits in the sub-ppb range Extremely sensitive for ultra-trace Hg Excellent in run precision Typically 1 2 % RSD
Precision - Why is This Important?

What does Precision mean?
Ability to get the same result for the same sample when measured multiple times
Usually measured as % RSD or sometimes, SD % RSD = (SD / Mean Result) * 100 Low values indicate good precision
For flame AA, expect < 1% RSD (Hydride AA < 2% RSD) For GFAAS, expect < 4% RSD
Why is this important?

User loses confidence in the system
What impacts on precision?

Lamp and burner/plasma stability
Sample introduction system Method parameters
27
AA Precision What to Check?

Lamp properly aligned?
System stabilized?
Allow 5-10 mins. warm-up for lamp/burner before analysis
Sample Introduction
Nebulizer uptake rate adjusted High uptake rate means great sensitivity and worse precision Impact bead adjusted correctly
Burner position optimized?

Mixing paddles fitted? Measuring at an appropriate concentration Close to the detection limit, noise is high and precision/accuracy is impacted
28
Accuracy - Why is This Important?

What does Accuracy mean?
Ability to get the right answer for the sample
Heavily dependent on operators skill
Why is this important?

User loses confidence in the system Your reputation
Customers question the results Poor performance in round robin comparisons
How do You Confirm Accuracy?

Check the result for a prepared standard
Measure a certified reference material

Use other quality control checks to check analysis
29
Accuracy What to Check?

Calibration standards properly prepared?
See earlier recommendations important to match to samples, prepare accurately and use them fresh
Any interferences impacting on results?

Use matched standards or standard additions For AA - use high temperature N2O/acetylene flame + appropriate matrix modifiers
Precision optimized
Optimum signal to noise performance improves accuracy
Measuring at an appropriate concentration Close to the detection limit, noise is high and precision/accuracy is impacted
30
Sample Throughput What to Check?

Samples fully digested?
No excess particulates in the sample that may cause blockage
Sample Introduction System optimized?

Capable of handling the TDS levels in the sample
Burner cleaned and ready for analysis?
Method parameters optimized

Pre-read delay time is appropriate optimized Read time is appropriate for the expected concentration Use a longer measurement time at low concentrations Rinse time is appropriate
Use a faster measurement technique like Fast Sequential AA
31
Flame AA Recommended Maintenance Schedule

Daily: Empty waste container
Check exhaust system

Clean burner compartment & instrument Check the gas delivery pressures & cylinder contents (esp. acetylene) Check the nebulizer uptake rate and burner condition Weekly: Clean burner (or earlier if required)
Disassemble flame atomization system and clean

Check condition of O rings and impact bead (no pitting)
Monthly:
Clean windows in sample compartment
Furnace AA Rec. Maintenance Schedule

Daily:
Empty waste container Check exhaust system
Check condition of the graphite tube replace as necessary

When replacing the tube, check the condition of the electrodes Clean the workhead around the sample injection hole Check dispensing capillary free and syringe Top up rinse reservoir as required Check the gas delivery pressures & cylinder contents
Weekly:
Check and clean furnace workhead windows (if required)
33
Hydride AA Rec. Maintenance Schedule

Daily: Empty waste container
Check pump tubing for stretching, deformation or severe discoloration

Release after each analysis Check connections to the reaction coil
Clean the absorption cell (soak in nitric acid)

Clean any spills and wipe the pump unit Weekly: Replace and condition the absorption cell (or earlier as required) Check the rollers rotate freely
34
Overview - Key Consumables for AA

All instruments:
HC lamps AA standard solutions
Flame AA systems:
Glass impact beads, burner cleaning strips, nebulizer components, capillary tubing, burners etc Ionization suppresant / buffer solutions With the SIPS dilution system SIPS pump tubing and transfer tubing With an autosampler - sample tubes, racks, probes and transfer tubing
Graphite furnace AA systems:

Graphite tubes
Sample vials, dispensing capillary and syringe for autosampler

Matrix modifiers
Vapor generation AA systems:

Quartz atomization cells
Peristaltic pump tubing

Connecting tubing
35
Flame Atomizer - Mark 7 Design

Key consumable items requiring frequent replacement:
O rings Glass impact beads Burner cleaning strips Nebulizer capillary kit Nebulizer venturi kit Capillary tubing Nebulizer cleaning wire Liquid trap assy Mixing paddles Burners
Where to find ordering details?

36
On-line help in the SpectrAA S/W Agilent website dedicated webpage: Mark 7 Spares Agilent Quick Reference Guide for AA Agilent Atomic Spectroscopy Supplies Catalogue
Where to Find the Right Consumable?

Analytical Consumables: Consumables & Supplies 1-800-227-9770 (Option 1,1) www.agilent.com/chem/contactus Agilent Assist: Instrument Sales &Services 1-800-227-9770 (Option 1,3) www.agilent.com/chem/contactus
On-Line resources:
Atomic Absorption Supplies Mark 7 Sample Introduction Spares
ICP-OES Parts & Supplies Portfolio

ICP-MS Supplies Instrument Parts & Supplies FAQs Atomic Spec. Application Notes Agilent Quick Reference Guide for AA (pub. # 5990-9476EN) Agilent Atomic Spec. Supplies Catalogue (pub. # 5990-8767EN) Agilent Consumables Catalogue (pub. # 5990-6674EN) Instrument User Manuals
37
Summary To Achieve Quality Data

Most instrument failures occur in the sample introduction area Includes
Burner Spray chamber Nebulizer All tubing Drain Assembly
Improper maintenance of this area can result in poor data quality
Frequently less experienced analysts can fail to recognize problems resulting in productivity losses
Establishing maintenance procedures can prevent problems
38
Questions?
Agilent MP-AES
Agilent AAS
Agilent ICP-OES
Agilent ICP-MS
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Guidelines for Troubleshooting and Maintenance of AA Systems

AA Maintenance & Trouble Shooting Apr. 2012

Todays Agilent: Atomic Spectroscopy

Graphite Furnace AAS

AAS instruments can be flame only, furnace only, or combined (switchable)

AA Maintenance & Trouble Shooting Apr. 2012

Agilents Atomic Spectroscopy Portfolio - Features

Lowest running cost

Trace levels at lowest price

AA Maintenance & Trouble Shooting Apr. 2012

Common AA Problems Reported by Customers

Poor Sample Throughput

AA Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity - What Impacts This?

Remember SMCQ Or System Must Create Quality

AA Maintenance & Trouble Shooting Apr. 2012

Sensitivity Quality of Standards

How are they prepared?

How are they stored?

Stabilize with acid low pH ensures better stability

AA Sensitivity Sample Introduction

Optimum viewing height for Ca

AA Maintenance & Trouble Shooting Apr. 2012

AA Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity Sample Introduction

Impact bead position

AA Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity Method Parameters

Wavelength/Slit selection and Lamp current

Nitrous Oxide/Acetylene Flame Stoichiometry

AA Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity System Cleanliness

Sample Introduction System

AA Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity Rec. Settings

For highest flame AA sensitivity:

For high TDS samples:

Use wide bore capillary tubing (to reduce chance of blockage)

Agilent Flame AA Performance Benefits

Tunable performance means

Best precision: < 0.5 % RSD using 10 x 5 s readings

Fast change-over to furnace operation (manual - < 30 s)

AA Maintenance & Trouble Shooting Apr. 2012

GFAA Sensitivity Sample Introduction

AA Maintenance & Trouble Shooting Apr. 2012

GFAA Sensitivity Sample Introduction

Choice of inert gas impacts sensitivity

AA Maintenance & Trouble Shooting Apr. 2012

GFAA Sensitivity Correct Capillary Alignment

Pipet tip too high!

Pipet tip too low!

Ensure there is no liquid inside the capillary tip after dispensing

Sample should remain as a drop in the centre of the tube

17 AA Maintenance & Trouble Shooting Apr. 2012

GFAA Sensitivity Method Parameters

Ensure inner gas flow off just prior to atomization

AA Maintenance & Trouble Shooting Apr. 2012

Automated Furnace Method Optimization

GFAA Sensitivity Method Parameters