VOC Sampling and Analysis

David Shelow
US EPA – OAR – OAQPS
Ambient Air Monitoring Group

National Air Monitoring Meeting

May 2012

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 Topics
• Sampling media – canisters, tubes, bags
• Making Standards
• Preconcentration & Analysis – GC/MS
• Canister cleaning
• Canister cleanliness testing
• AutoGCs

2
 Sampling
– Canisters (WholeAir)
• SUMMA, Silco/Silonite
• Active sampling (aka non-passive)
• Passive sampling
– Tubes
• Active
• Passive
– Bags
• Chambers for filling

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 Methodology
• EPA Compendium Toxic Organic Methods
• VOCs (C2 to C12)
– TO-14 (canister based non-polars)
– TO-15 (canister based with addition of polars)
– TO-17 (tube based, thermal desorbtion)
• VOCs not criteria pollutant so no FRMs, just
“guideline” methods
• Performance based
• Old….ASTM is written more updated
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methods, EPA has no plans to update.
 Canister Sampling
• Grab sampling
– Emergency response
– Capturing event
– Qualitative
– Fills in seconds up to minutes
• Integrated Sampling/Time weighted
average (TWA)
– 24 hr most common
– 3hr and 8hr sampling for patterns
5
 What is a Canister?
• Typically 304L grade stainless
• Whole Air sampling – representation of the
ambient air
• Should be leak free to a leak rate of 4 x 10-9,
canister should hold vacuum 30 days.
• SUMMA is an electropolished Stainless
R

Steel
• Silco/Silonite – is amorphous silica coated
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• Registered trademark of Molectrics Corp
 Canister Valves
• Most critical part of canister
• No soft seat, Must have a metal seat, what
does that mean?
• Very difficult for metal seats to seal
repeatedly. Easily damaged.
• Expensive (b/c seat)
• SS wetted path
• Temperature limitation during cleaning
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8
Entech Canister valve

•Repairable
•Packless
•Low internal volume
•SS wetted pathway
•Can be silica lined

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 TWA Canister Sampling
• Passive or non-passive (active)
• Passive is commonly used when no power
source is available.
• Use vacuum of canister to pull sample into
canister.
• Must be stainless steel wetted pathway.
• Flow restriction kits commercially available

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 Passive Sampling kits
• Critical Elements:
– Sapphire Orifice to restrict flow to flow range
– SS Diaphragm to regulate flow (to a point)
– Filter to remove particulates
– “candy cane” to prevent rain entering
– Vacuum gauge

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Passive Sampling Kits
Critical Orifice
(sapphire)

Particulate Filter

Vacuum Gauge

Internal SS
diaphragm

Easy Connection to canister 12

valve
 Critical orifice flow ranges
Critical orifice diameter vs. flow rate.

• Orifice Diameter Flow Rate Range Canister Volume / Sampling Time

• (in.) (mL/min.) 1L 3L 6L 15L
• 0.0008 0.5–2 24 hr. 48 hr. 125 hr. —
• 0.0012 2–4 4 hr. 12 hr. 24 hr. 60 hr.
• 0.0016 4–8 2 hr. 6 hr. 12 hr. 30 hr.
• 0.0020 8–15 1 hr. 4 hr. 8 hr. 20 hr.
• 0.0030 15–30 — 2 hr. 3 hr. 8 hr.
• 0.0060 30–80 — — 1.5 hr. 4 hr.
• 0.0090 80–340 — — 0.5 hr. 1 hr.

• Select orifice size based on flow range/sampling time interval

• Dial the exact flow rate you want.

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Setting flow rate on passive sampling kits

1. Pull air thru flow controller

2. Using a good flow meter, set
flow by adjusting piston
3. Replace cap to protect piston
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 Passive Sampling kits
• No power needed.
• Uses vacuum of canister to pull sample
• However, flow controller maintains
constant flow to a point.
• That point is around 7”Hg vacuum.
• Therefore, to have a valid sample the
canister should not be allowed to come to
ambient pressure (0 psig).
• Stop sampling prior to canister reaching 15
7”Hg vacuum. (Subambient sampling)
Passive Sampling Kit flow controllers

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 Subambient Sampling
Advantages Disadvantages
• Mechanical • Low flow rate
failure • Sample is under
eliminated vacuum
• Contamination • Preconcentrators
minimized. struggle with this
• Pressurizing
• Less potential
results in dilution of
for leaks
sample
• No power req. 17
 Non-Passive or Active sampling
• Pressurized sampling.
• Canister sampler will “push” or “pump” air
into the canister at a constant flow rate.
• You don’t have to stop at 7”Hg vacuum,
can actually put positive pressure sample.
• Ensure constant flow rate
• Can collect more than 6 liters of air.
• Requires electricity
• Can do multiple canisters 18
Multi Canister Samplers - Active

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 Pressurized Sampling
Advantages Disadvantages
• Sample transfer • Pump is a source
is easier to of contamination
preconcentrator • Lots of leak
• Multiple canister potential, many
sampling (3hr) connections.
• Mechanical failure
• Difficult to clean
once contaminated.
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 The Analytical System

Preconcentrator

MSD

GC

Autosampler
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 Preconcentrator
• Purpose - to concentrate the sample.
• Cryogenically cooled (liquid N2)
• Thermally desorbed
• Water and CO2 management is key
• Pumps capable of sampling in subambient
canisters
• Only a few commercially available.
• Multiple traps.
• Autosamplers for 16 canisters is typical. 22
 GC/MSD
• GC column should be a fused silica High
resolution capillary column for VOCs
(different column for semi-volatiles)
• Pumping capacity of Mass Spec
determines ID of column
• Mass Spec is capable of indentifying
compounds using spectral analysis
• Some labs split effluent of GC to two
detectors (FID)
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GC/MSD

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 TO-15 Chromatogram 1. Propylene
2. Freon -12 (dichlorodifluoromethane)
®

3. Chloromethane
4. Freon -114 (dichlorotetrafluoroethane)
®

5. Vinyl chloride
6. 1,3-Butadiene
7. Bromomethane
8. Chloroethane
9. Carbon disulfide
10. Acetone
11. Freon -11 (trichlorofluoromethane)
®

12. Isopropyl Alcohol

13. 1,1-Dichloroethene
14. Methylene Chloride
15. Freon -113 (1,1,2-trichloro-1,2,2-trifluoroethane)
®

16. trans-1,2-Dichloroethene
17. 1,1-Dichloroethane
18. Methyl tert-butyl ether
19. Vinyl acetate
20. Methyl ethyl ketone
21. cis-1,2-Dichloroethene
22. Hexane
23. Chloroform
24. Ethyl Acetate
25. Tetrahydrofuran
26. 1,2-Dichloroethane
27. 1,1,1-Trichloroethane
28. Benzene
29. Carbon Tetrachloride
30. Cyclohexane
31. 1,2-Dichloropropane
49. Bromoform 41. Methyl butyl ketone 32. Trichloroethylene
50. Styrene 42. Dibromochloromethane 33. Bromodichloromethane
51. o-Xylene 43. 1,2-Dibromoethane 34. 1,4-Dioxane
52. 1,1,2,2-Tetrachloroethane 44. Tetrachloroethylene 35. Heptane
53. 4-Ethyltoluene 45. Chlorobenzene 36. cis-1,3-Dichloropropene
54. 1,3,5-Trimethylbenzene 46. Ethylbenzene 37. Methyl Isobutyl Ketone
55. 1,2,4-Trimethylbenzene 47. p-Xylene 38. trans-1,3-Dichloropropene
56. 1,3-Dichlorobenzene 48. m-Xylene 39. 1,1,2-Trichloroethane
57. Benzyl chloride 40. Toluene
58. 1,4-Dichlorobenzene
59. 1,2-Dichlorobenzene
60. 1,2,4-Trichlorobenzene
61. Hexachloro-1,3-Butadiene
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 Mass Spec
• Full Scan (TIC)
– Scans multiple scan ranges every microsecond
– Common VOC scan range 35 – 250amu
– Reports area of primary quantitation ion
– Use this mode for Emergency response!!
• Selected Ion Mode – SIM
– Certain masses within a retention time window.
– Much more sensitive

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 VOC Standards Prep

• Purchase commercially available

standards at concentrations of 1ppm or
higher.
• Dilute working levels using a dynamic
dilutor.
• Humdification is extremely important.
>35%RH.
• Measure humidity of diluent gas to ensure
proper %RH
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 How to Humidify Canisters for Stds
• Inject H2O with syringe (gas tight)
• The dynamic dilutor have small vessels
• Make your own
– Erlenmeyer flask
– Solvent bottles
– Dryrite vessels
• Measure %RH output

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 Canister Cleaning
• The most important aspect to VOCs.
• Everybody’s definition of ambient air is
different.
• Source level samples will contaminate the
whole cleaning and analytical system.
• Keep a canister log of each canister.
• Batch test vs individual testing.

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 How to clean a canister
• Pressure and evacuation with humidified
air or nitrogen. How long?
• Heat canisters but at what temperature?
• Valve’s are the limiting factor.
• Above 100oC, creating steam. Is that good
or bad?
• Steam is not a good thing for fused silica
lined canisters.
• Most cleaning cycles run 4-8hrs. 30
How to Heat Canisters during Cleaning
• Ovens

• Heat bands

• Heating jackets

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 How to Humidify Canister Cleaning
• Make your own
– Erlenmeyer flask
– Solvent bottles
– Dryrite vessels

• Measure %RH output.

• Cold trap to collect contaminate and
prevent oil vapors from pump.
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 Canister Cleanliness Testing
• Typically batch testing is done.
– Eg. 2 out of 16
• Which canisters do you test?
– Typically the canisters that had the highest
values during analysis testing.
• TO-15 cleanliness spec is 0.2ppbv per
component….this is not low enough (10-6 risk
level)
• Can you test every canister?
• Recommend testing over time (2-3 weeks) 33
 What about Canister stability?
• It is good practice to test canisters for
cleanliness over time periodically…
• It is also good to test canisters for stability
as well.
• What does that mean? Place a know
concentration of TO-15 into the canister
and test over time to measure stability.
• The results tell a story.
• Log the results. 34
 Thermal Desorbtion Tubes
• Active
– Pumps pull air thru at a constant rate
• Passive
– Diffusion over time eg. 2 weeks
• Advantages and disadvantages
• Thermally desorbed
• Can get higher MW range

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 TO-17 Chromatogram
C6 to C16 VOCs

2-Butoxyethanol

Naphthalene
Benzene Phenanthrene

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 Active Tubes
• Pump required
• Multi bed tubes
– Tenax
– Carbotrap
– Carboxen
• Thermally desorbed
• Can be reused
• Markes, Perkin Elmer, Dynatherm
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 Diffusive Badges
• Diffusive badges for certain VOCs
– SKC, Radiello, Markes Int.
• CS2 Solvent extracted
• Thermally Desorbed

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 Tubes
Advantages Disadvantages
• Larger MW range • One shot
• $ - less exp • Breakthrough
• Effect Temp, %RH
• Longer sampling
times • Background
• Match adsorbents
with compounds

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 AutoGCs
• Many advancements in last 10 years
• Metal columns (unbreakable)
• Smaller detectors
– Photo Ionization Detectors (PID)
– Flame Ionization Detectors (FID)
– No MSD versions yet
• More efficient trapping (preconcentration)
• Single and dual column configurations
• Better software for data analysis, QA 40
 AutoGCs for VOCs
• No Cyrogenics
• Sorbent traps or sample loops
• Hydrocarbon range dependent
• One column for C2-C6 VOCs
• A different column for C6-C12 VOCs
• Identification by Retention time
• Backflushing capabilities

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 AutoGCs Manufacturers
• SynSpec
• American Ecotech
• Perkin Elmer ITD
• OI Corp

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C2-C6 Cgram

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 Summary
• Canisters are still most common media for
VOCs sampling
• Canister cleanliness is crucial
– Test canister over time
– For cleanliness and stability
• GC/MSD – Full Scan mode vs SIM
• Tubes can collect in VOC/SVOC range

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 Contact Information
• Questions/Comments
• Contact me:
– Dave Shelow
– 919-541-3776
– [Link]@[Link]

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