AA Troubleshooting and Maintenance

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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)

AA Maintenance & Trouble Shooting Apr. 2012

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

AA Maintenance & Trouble Shooting Apr. 2012

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 Maintenance & Trouble Shooting Apr. 2012

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

AA Maintenance & Trouble Shooting Apr. 2012

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


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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 Maintenance & Trouble Shooting Apr. 2012

AA Sensitivity Compromise

Ca N20/C2H2 Air/C2H2

Higher Sensitivity

Lower Noise

AA Maintenance & Trouble Shooting Apr. 2012

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 Maintenance & Trouble Shooting Apr. 2012

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
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Nitrous Oxide/Acetylene Flame Stoichiometry

Lean

Stoichiometric

Rich

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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)


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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)

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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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

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AA Maintenance & Trouble Shooting Apr. 2012

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
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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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

Hydride AA Sensitivity Sample Introduction


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

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AA Maintenance & Trouble Shooting Apr. 2012

Hydride AA Sensitivity Sample Introduction


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)

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AA Maintenance & Trouble Shooting Apr. 2012

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
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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
AA Maintenance & Trouble Shooting Apr. 2012

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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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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
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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)

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AA Maintenance & Trouble Shooting Apr. 2012

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

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AA Maintenance & Trouble Shooting Apr. 2012

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
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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?



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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
AA Maintenance & Trouble Shooting Apr. 2012

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
AA Maintenance & Trouble Shooting Apr. 2012

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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

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AA Maintenance & Trouble Shooting Apr. 2012

Questions?
Agilent MP-AES

Agilent AAS

Agilent ICP-OES

Agilent ICP-MS

The Market Leaders in Atomic Spectroscopy


39 AA Maintenance & Trouble Shooting Apr. 2012

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