# Presentation: 217766

## Experiences with Wet Test Methods for Formaldehyde

- Rick Szekeres
- Environmental Chemist
- Pennsylvania Department of Environmental Protection
- http://www.dep.state.pa.us/dep/deputate/airwaste/aq/source/sts.htm

## Brief History of Wet Test Methods

- 1990 EPA Method (EPA/600/3-90/005)
- Constant Rate Sampling; DNPH
- 1991 BIF Method 0011 (SW-846)
- Isokinetic Sampling; DNPH (opt. breakthrough check)
- NCASI Chilled Impinger Methods
- Constant Rate Sampling (400±50 cc/min); Water
- CI/SG/PULP-94.02 (for pulp & paper mills)
- No filter; 2 Impingers, first empty
- CI/WP-98.01 (for wood products mills)
- Hot probe/filter; two impingers
- IM/CAN/WP-99.01 (for wood products mills)
- Hot probe/filter; 3 Impingers, first with glass frit
- EPA Method 301 Validation

**Notes:**
NCASI Methods: formaldehyde collected in impingers, derivitized with acetylacetone, and analyzed by colorimetry.  The ’94 Method is validated for 40 CFR 63 Subpart S, the ’98 Method is validated without equivalency, and the ’99 Method is self-validating.

## Allegheny Particleboard Tests

- 06/94 1990 EPA Method (constant rate)
- 08/94 BIF Method 0011 (isokinetic)
- Board Press & Cooler results were substantially lower
- Why were the results so different?
- Process Variability?
- Difference in Sampling Rate?
- Breakthrough, despite unreacted DNPH?

## Yorktowne Department Tests

- Waste Wood-Fired Boilers w/common stack
- 5 MMBtu/hour heat input (per unit)
- Cyclones used for particulate control
- 07/96 BIF Method 0011
- 2 impingers, each with 150 mL of DNPH
- 31.6% of CH2O in last impinger; probable breakthrough
- 10/96 BIF Method 0011
- 4 impingers, each with 150 mL of DNPH
- 0.1% of CH2O in last impinger; no breakthrough
- Mass emission rate was 2.7x higher
- CH2O emissions much higher than AP-42 Factor
- 2 lbs/ton versus 0.019 lbs/ton (assuming HHV of 8500 btu/lb)

## Wood-Mode Department Tests

- Virgin or Waste Wood-Fired Boiler
- 30MMBtu/hour heat input
- Cyclone used for particulate control
- 08/96 BIF Method 0011
- 4 impingers, each with 150 mL of DNPH
- 0.1% of CH2O in last impinger; no breakthrough
- Fuel had no appreciable impact on CH2O emissions
- Some aldehyde emissions increased for waste wood
- CH2O emissions much higher than AP-42 Factor
- 5 lbs/ton versus 0.019 lbs/ton (assuming HHV of 8500 btu/lb)

**Notes:**
Acetaldehyde and valeraldehyde emissions increased when waste wood was fired.

## Testing at MDF Plants(BIF Method 0011)

- 10/97 Allegheny MDF
- 57.3% of formaldehyde in last (2nd) impinger
- Probable breakthrough
- 11/97 MacMillan Bloedel Clarion
- 4.4% of formaldehyde in last (3rd) impinger
- No breakthrough

## Testing at MDF Plants(NCASI Method CI/WP-98.01)

- 12/98 Masonite Corporation
- 2-58% of formaldehyde in last (2nd) impinger
- 10% for Die Form Press
- 38% for Resin Blender
- 46% for Felter Scrubber
- 58% for Board Cooler
- 46% for First Stage Dryer
- 2% for Second Stage Dryer
- Probable breakthrough when sampled at 650 cc/min

**Notes:**
Methanol breakthrough for Resin Blender (25%) and 2nd Stage Dryer (46%).  Also, the method requires sampling at 350-450 cc/min.  Moisture was apparently not a factor.

## Testing at MDF Plants(Method 25C vs. Method 25A)

- Misreporting or Underreporting
- Non-Simultaneous Testing at Two Facilities with Similar Production Capacity
- Results from one facility appeared to be twice as high as from the other facility
- Why were the results so different?
- Reporting Issues
- Differences in Operating Conditions

## Issues of Concern

- Do the various test methods produce data that is comparable?
- If the test methods are not comparable, how does one decide which procedure is appropriate?
- Is breakthrough a problem?
- Is formaldehyde being accounted for?
- Would audit samples help validate the data?

## Questions or Comments?