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Effects of Aging on Surface Inertness and Analyte Recoveries in SUMMA Passivated and Fused Silica Lined

Canisters

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Objectives

• Test Canisters from 4 Manufacturers for the Relative Aging Effects of Repeated Sampling on TO14 Standard Recoveries

• Repeat Test After Exposure to 1% Ozone for 8 hours

• Test Aged Canisters using a Spectra Gas TO15 Mixture

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Canisters in Study

• 4 Manufactures - 2 SUMMA, 2 Fused Silica Lined

• 2 Cans from Each Manufacturer

• SUMMA cans labeled S1 - S4

• Fused Silica Lined Canisters Labeled FS1-FS4

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Silonite Coated 6L Canisters

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SiloniteTM Coating of Canisters

• Improves Recovery of Reactive Compounds

• Increases Range of Compounds Amenable to Canister Sampling and Analysis

• Compounds Containing:

– Sulfur

– Nitrogen

– Oxygen

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Analysis of Cylinder - 9 December 1999

2.52 ppm

2.65 ppm

2.54 ppm

Analysis of Mini Canister #1086 - 10 December 1999

2.56 ppm

2.44 ppm

Analysis of Mini Canister #1087 - 10 December 1999

2.57 ppm

2.56 ppm

Let time pass....

Analysis of Mini Canister #1086 - 20 January 2000

2.46 ppm

2.53 ppm

Analysis of Mini Canister #1087 - 20 January 2000

2.37 ppm

2.47 ppm

40 Day Formaldehyde Stability in Silonite Coated MiniCan

Data Courtesy ofDr. Daniel Riemer,NCAR

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5 . 0 0 10 . 0 0 1 5 . 0 0 2 0. 00 2 5 . 0 0 30 . 0 0

5 0 0 0 0 0

1 0 0 0 0 0 0

1 5 0 0 0 0 0

2 0 0 0 0 0 0

2 5 0 0 0 0 0

3 0 0 0 0 0 0

3 5 0 0 0 0 0

4 0 0 0 0 0 0

T im e -- >

A b u n d a n ce

T I C : 9 9 1 2 1 0 0 2 . D

5 . 0 0 10 . 0 0 1 5 . 0 0 2 0. 00 2 5 . 0 0 30 . 0 0

5 0 0 00 0

1 0 0 0 0 0 0

1 5 0 0 0 0 0

2 0 0 0 0 0 0

2 5 0 0 0 0 0

3 0 0 0 0 0 0

3 5 0 0 0 0 0

4 0 0 0 0 0 0

T i m e- - >

A bu nd a n ce

T I C : 9 9 1 2 1 0 0 4 . D

New Silonite Canister Used SUMMA Canister

10 PPB TO14 Std

5 PSIGHolding Time - 1 Day

1-Day TO14 Stability Test @ 10PPB

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Clean up TestBlank Test After 100 PPB TO14 Exposure

New Silonite Canister Used SUMMA Canister

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Canister Study• Test all Canisters at the Beginning of Study

– Fill Canister with 10 PPB TO14 Mix

– Equilibrate 1 Day and Analyze

• Clean All 8 Canisters Together (3 cycles at 100 C)

• Fill Canisters with Ambient Air using Glass Filtered Grab Sampler

• Wait 1 Day, then Repeat Cleaning

• Perform Operation 30 Times

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8 Canister Cleaning System

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Glass Filtered Grab Sampling

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Standard Introduction and Analysis

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•Automates the GC analysis of gas phase samples

•Complete heating of sample flow path. Easily accessed for trap and tubing replacement

•Multiple trapping stages allow matrix to be eliminated before GC injection

7100 3-Stage Preconcentrator

7100 Preconcentrator

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InternalStandard

CalibrationStandard

Sample

Glass Beads Tenax

Cryogen in

N2, O2H20, CO2

Focuser

ToGC

Helium

PUMPMFC

Helium Carrier

7100 Preconcentration and Matrix Management

3-Stage Preconcentration

SampleHeadspace

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3 .5 0 3 .55 3 .6 0 3 . 6 5 3 .70 3 .7 5 3 . 80 3 .5 8 3 . 9 0 3 . 95

7 5 0 0 02 6 0 0 0

2 5 0 0 0

2 4 0 0 0

2 3 0 0 0

2 2 0 0 0

2 1 0 0 0

2 0 0 0 0

1 9 0 0 0

1 8 0 0 0

1 7 0 0 0

1 6 0 0 0

1 5 0 0 0

1 4 0 0 0

1 3 0 0 0

1 2 0 0 0

1 1 0 0 0

1 0 0 0 0

9 0 0 0

8 0 0 0

7 0 0 0

6 0 0 0

5 0 0 0

4 0 0 0

3 0 0 0

2 0 00

1 0 0 0

0

7 0 0 0 0

4 5 0 0 0

6 5 0 0 0

5 0 0 0 0

4 0 0 0 0

3 0 0 0 0

2 5 0 0 0

3 5 0 0 0

2 0 0 0 0

1 5 0 0 0

1 0 0 0 0

5 0 0 0

6 0 0 0 0

5 5 0 0 0

E than o lm /z 4 54 .35 m in0 .17 ppb .

M ethan o lm /z 3 13 .67 m in .0 .49 ppb

Fast Injection and Proper Water Management Minimizes Tailing of Polar Compounds

Column: HP1, 60m, 0.32mm ID, 1um film.

Flow rate: 1.5 ccm

Carrier: He

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New SILONITE Coated Canister Before Study

Concentration - 10 PPBPressure - 10 PSIGVolume - 400 CCWater Management - Microscale Purge and TrapInstrumentation 7100/5973Column - DB1Starting Temperature - 35 deg. CScan - 30-185, 6 min, then 34-270 amu

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S1 S3

10 PPB/10 PSIG TO14 , 1 Day Stability - SUMMAs

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FS 1 FS 3

10 PPB/10 PSIG TO14 , 1 Day Stability - FSL Cans

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S1 S3

10 PPB/-4 PSIG TO14 , 1 Day Stability - SUMMAs

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10 PPB/-4 PSIG TO14 , 1 Day Stability - FSL Cans

FS 1 FS 3

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FS 1

10 PPB/-4 PSIG TO15 , 1 Day Stability - SUMMAs

FS 3

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10 PPB/-4 PSIG TO14 , 1 Day Stability - FSL Cans

FS 1 FS 3

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Possible Reasons for Poor Recoveries in Canisters

• Coating or Surface Treatment was not Initially Inert

• Welds have Active Surfaces

• Contaminants have been Introduced

– Particulates

– Semi-Volatiles

– Reaction Products

– Dirt

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Pressurized Field Sampling

• Causes Condensation of Water in transfer lines and Canisters

• Water can Promote Polymerization Reactions

• White Deposits Found in Bottom of Canisters which were Repeatedly Sampled to Positive Pressure in the Field

• Not Required for Today’s Samplers / Analyzers

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Removing Heavy Contaminants from Canisters

• Evacuate Canisters

• Use Vacuum to Draw in 200 cc of DI Water

• Heat to 60 deg. C for 8 Hours (or Overnight)

• Pressurize Cans to 20 psig

• Shake Canister Well, Invert, Blow out Water

• Perform Normal Cycle Cleaning

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Conclusion• Both SUMMA and Fused Silica Lined Canisters Showed no Detectable

Loss of Inertness after 30 Samplings of Ambient Air

• Although Individual Recoveries of TO15 Standard Varied, Both Canister Types Provided Good Recoveries of Spectra Gas TO15 Compounds

• Ozone Exposure did not Change Recoveries

• Canister Cleanliness is Extremely Important. Canisters Should be Checked Regularly for Analyte Recovery

• If Recoveries are Found to be Low, Enhanced Cleanup Techniques are Available to Remove Adsorbing / Absorbing Contaminants