State of California Air Resources Board
State of California Air Resources Board
SPECIAL ANALYSIS
VOLUME VI
1.0 SCOPE 2
3.0 DEFINITIONS 2
4.0 INTERFERENCES/LIMITATIONS 4
5.0.1 Instrumentation
5.0.2 Auxiliary Apparatus
5.0.3 Reagents
8.0.1 Calibration
8.0.2 Continuing Calibration Verification (CCV)
8.0.3 Control Charts
8.0.4 Environmental Chambers Temperature and Relative Humidity
8.0.5 Flow Rates
8.0.6 Replicates
8.0.7 Blanks
8.0.8 Sample Stability and Holding Times
PAGE REVISION DATE
Appendix A 17
FIGURES
1.0 SCOPE
This analytical method may achieve a detection limit of 0.6 ppb and an estimated
quantitation limit (EQL) of 3 ppb for formaldehyde.
A section of composite wood sized to meet the air flow and surface area
requirements as defined in the ASTM D6007-02 method is placed in the small
chamber within an environmentally controlled unit. Air is circulated through the
small chambers at a flow rate of 1.0 liter per minute (LPM) for 0.5 hours*. DNPH-
silica cartridges are placed on a sampling line from the small chamber to collect
emissions. The samples are eluted with 10 mLs of acetonitrile (ACN) then
analyzed using a liquid chromatograph with an ultraviolet detector at 360 nm.
3.0 DEFINITIONS
BLANK - a sample that has not been exposed to the sample stream in order to
monitor contamination during sampling, transport, storage, extraction, or
analysis. The blank is subjected to the usual analytical and measurement
process to establish a zero baseline or background value.
4.0 INTERFERENCES/LIMITATIONS
5.0.1 INSTRUMENTATION
5.0.3. REAGENTS
Enforcement Division (ED) staff collect and process the products, either
raw boards or finished goods following their prescribed SOP. Samples
may be prescreened for formaldehyde using a Field and Laboratory
Emission Cell (FLEC meter), when possible. Samples are brought to the
laboratory with chain-of-custody (COC) forms identifying each sample and
its screening concentration. If the sample identification information does
not match the COC record, ED staff must make corrections at the time of
delivery or the laboratory may refuse to accept samples until such
corrections are made. Samples are stored as received in separate
packaging at room temperature until conditioning is performed.
The area and cut size of the sample is dependent on the type of
composite. The size of the sample is based on the flow to area (Q/A) ratio
as described in Table 1 of ASTM D6007. Each small chamber has a
volume of 0.021m3 (20.32 x 20.32 x 50.8 cm). The air flow is 0.06 m3/hour
(the same as the sampling flow rate, 1 LPM) therefore, to meet the
specified Q/A ratio the size of the CWP samples are:
PB (particle board) - 180mm x 143 mm
HWPW (hardwood plywood) - 180mm x 143 mm
MDF (medium density fiberboard) - 180 mm x 90 mm.
Flow rates through the small sampling chambers are maintained using a
pump and flow controllers (Figure 1).
6.0.3 CONDITIONING
specifications. If the combined area of the cut edges is greater than five
percent of the surface area, the edges must be covered with aluminum
flex tape prior to conditioning.
Sampling consists of a 0.5 hour system purge and a 0.5 hour sample
collection as specified below.
Sampling in the small chamber is for 0.5 hour with an air flow of 1.0
LPM (0.06 m3/hour). The first 0.5 hour sampling using a blank pre-
sampling cartridge purges the chamber system. This cartridge is a
spent cartridge and may be reused for this purpose multiple times.
This cartridge is not analyzed. Changing the pre-sampling cartridge
on a monthly basis is recommended. This purge blank ensures
NLB SOP SAS20
Sampling and Analysis of Formaldehyde Emissions
Revision 1, November 2012
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3. Sampling
Sample extraction must be done within thirty days of sample collection per
the cartridge manufacturer’s recommendation. If this extraction hold time
is exceeded, results may be biased low and should be flagged or
invalidated.
Solvent blanks are analyzed with each batch of samples. The blank must
be free of interferences that may affect the formaldehyde peak. A solvent
blank is analyzed before and after the calibration and all other QC
samples, with every ten samples, before and after the calibration
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Sampling and Analysis of Formaldehyde Emissions
Revision 1, November 2012
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7.0.4 INSTRUMENTATION
8.0.1 CALIBRATION
1. Weekly
2. Daily
the CCV and all samples in the batch following the last valid CCV need to
be reanalyzed. A recalibration may be performed.
Control charts are used to show that the system (sampling, extraction, and
analysis) is within expected limits, to signal systematic departures, and to
identify inconsistencies in precision. Charts are created using the results
of the CCV analyses. Upper and lower control limits and warning limits
are established after at least 20 CCV values have been obtained. Control
limits are calculated as +3σ (+3 times the standard deviation) from the
mean of the multiple measurements and warning limits are +2σ (+2 times
the standard deviation). All CCV results must fall within the control limits.
Trends and exceedences must be evaluated for corrective action.
8.0.6 REPLICATES
8.0.7 BLANKS
The method blanks, solvent blanks, and cartridge blanks should have no
interfering peaks in the area of the formaldehyde that might cause
integration problems. One method blank (extraction blank) must be
prepared with each batch of samples extracted. Any concentrations
greater than the limit of detection (LOD) in the method blank are reported
but no blank correction is made.
data storage, data processing, and report generation. All changes made
to data contained in LIMS are electronically tracked.
Final reports generated by LIMS and submitted to clients will include the
following, based upon information provided by ED staff and through
laboratory protocol:
Conditioning information:
date performed,
temperature,
humidity,
duration,
conditioning background level
Sampling information:
date performed,
temperature,
humidity,
air flow rate,
duration,
testing background level
Analytical results with:
sample identification,
wood type,
analysis date
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Sampling and Analysis of Formaldehyde Emissions
Revision 1, November 2012
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Figure 1.1
Small Chamber Sampling System
Wasson-ECE Pump and Flow Controllers
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Sampling and Analysis of Formaldehyde Emissions
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Figure 1.2
Environmental Chamber
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Sampling and Analysis of Formaldehyde Emissions
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Figure 1.3
Samples in Environmental Conditioning Chamber
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Sampling and Analysis of Formaldehyde Emissions
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Figure 1.4
Taped Sample in Small Sampling Chamber
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Sampling and Analysis of Formaldehyde Emissions
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Figure 1.5
Environmental Chamber with Small Sampling Chambers Inside
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Sampling and Analysis of Formaldehyde Emissions
Revision 1, November 2012
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APPENDIX A
6/21/10
Approved by:
1. SCOPE
A section of composite wood sized to meet the air flow and surface area
requirements as defined in ASTM D6007-02 is placed in a small chamber within
a larger environmentally controlled chamber. DNPH-silica cartridges are placed
on a sampling line from the small chamber for 0.5 hours at a flow rate of 1.0 liters
per minute (LPM). The samples are eluted with 10 mLs of acetonitrile (ACN). A
liquid chromatograph with a ultra-violet detector at 360 nm is used for analysis.
3. INSTRUMENT REPRODUCIBILITY
The instrumental detection limit is based on US EPA MDL calculation. Using the
analysis of seven (7) replicates of a low-level standard (Table 1 above), the
method detection limit (MDL) and the estimated quantitation limit (EQL) for
formaldehyde is calculated by: MDL = 3.14*(std dev values), where std dev = the
standard deviation of the concentration calculated for the seven replicate spikes.
The instrumental MDL is 0.02 µg/sample (0.002 µg/mL). EQL, defined as
5*MDL, is 0.10 µg/sample (0.01 µg/mL) based on a 10.0 mL extraction volume.
The instrumental MDL and EQL corresponds to 0.6 ppb and 3.0 ppb,
respectively.
6. CONDITIONING TIME
Preliminary analysis was with boards identified as M37, a medium density fiber
board. The board was a 4 x 8 foot panel with various cuts sent to the laboratory.
The boards were tested prior to conditioning (day 0), then at 1, 2, 3, 4, 7, and 10
days. Figure 1 graphs the results over the 10 days of sampling. Averaging the
data for a formaldehyde result to the whole panel (dotted line in graph) ranged
from 237 ppb for day 1 to 220 ppb for day 7. The overall percent difference for
the average between day 1 and day 7 is 7.2%. The percent difference between
day 1 and day 7 for the individual boards averaged 6.6%, ranging from 0.6-
13.2%. The difference between the 7 day and 10 day sampling averaged 6.2%,
ranging from 2.6-9.6%.
ppb after day 1, and 101 ppb after day 7. The concentration of the formaldehyde
for the pairs 3/4, 5/6, and 7/8 varied depending on the board and the location of
the sample within the board. The change in concentration between day 1 and
day 7 conditioning ranged from 1.6-21% for all the boards. The concentration for
the split boards, 9, averaged 211-236 ppb at day 1 and 152-171 ppb at day 7 (PB
44-(A,B,C)9 only had 3 days, with 220 ppb. These boards had the largest
difference in concentrations between the day 1 and day 7 ranging 24-27% for the
7 days.
The wide range of formaldehyde values may also be a result of where in the 4 x
8 panel the smaller samples are taken. Analysis of a series of HWPW boards
early in the method development shows a wide variation in the concentration of
formaldehyde across the boards as well as between boards. Figure 7 shows the
layout of the boards cut for the analysis. The average formaldehyde
concentration for the boards ranged from 48.3 ppb to 78.5 ppb. These are
boards that were purchased at the same time, same location. The variation
within a board ranges to 30%. What is observed is that formaldehyde
concentration can vary dramatically within and between boards from the same
processing lot.
The conditioning time of overnight or 18-24 hours for the boards for analysis was
chosen to maximize throughput of samples for a production lab. A 2 hour
conditioning time as mentioned in the ASTM would be too short to be efficient in
production. A seven day conditioning time is prohibitive time-wise for analysis in
a efficient manner. From the data of the boards a greater variation is observed
within boards than between a day 1 and day 7 analysis.
Another set of M40 boards were placed between M39 boards in a 9 mil plastic
bag for a week prior to testing. The M40 boards were then removed and
conditioned 24 hours for testing. The boards were placed back in the
conditioning chamber for another 24 hours and tested. Table 3 shows the results
of the testing of these boards.
A third set of contamination testing was done where edge piece of M40 were
received “boxed” in with M39 pieces to maximize exposure to the higher boards.
Another set of M40 boards were received alternating between M39 boards. The
samples were conditioned 24 hours and tested. The results for these samples
are reported in Table 4.
NLB SOP A
Sampling and Analysis of Formaldehyde Emissions
Revision 1, June 2010
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The baseline concentration of formaldehyde for M40 boards averaged 17.3 ppb
after the 24 hour conditioning. Concentrations were higher by over 50% when
the boards were exposed to the higher emitting boards while in the conditioning
chamber. The formaldehyde concentration is higher for any of the boards that
were exposed for a longer period of time or placed in closer proximity with the
high boards. The data does indicate that the potential of cross contamination
may be an issue with samples for enforcement if packaged together. There will
be multiple samples from the same source or product; the boards will be
packaged individually, which should minimize any storage contamination. The
lab will attempt to condition samples from the same product or batch and any
potentially high emitting products will be conditioned with similar ones.
8. Storage Stability
A series of samples cut from boards identified as M35 and PB36 were analyzed
over a 9 month period to see how the boards held up in long term storage. A set
of 3 boards from each panel was brought in by Enforcement periodically over the
time for analysis. The results of the analysis are shown in Figure 8. Over the 9
month study the concentration of formaldehyde in M35 dropped by 28%, going
from 143 ppb to 103 ppb. The concentration in PB36 showed a similar loss
going from 158 ppb to 106 ppb, a loss of 33%. The analysis showed the boards
to be fairly stable for about 4 months before dropping. What the study suggests
is that boards left at room temperature for extended length of time (more than 4
months) may result in lower formaldehyde concentrations when tested.
9. Safety
The procedures discussed here do not address all of the safety concerns
associated with chemical analysis or the mechanical preparation of the boards. It
is the responsibility of the analyst to establish appropriate safety and health
practices. For hazard information and guidance refer to the material safety data
sheets (MSDS) of any chemicals used in this procedure.
NLB SOP A
Sampling and Analysis of Formaldehyde Emissions
Revision 1, June 2010
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350
300 M37-B1/B2
M37-C1/C2
250
H2CO ppb
M37-F5/F6 M37-D11/D12
200
M37-E5/E6
150
M37-C11/C12
100
0 1 2 3 4 7 10
Days Conditioned
60
55 M41a6
M41d4
50
M41f2
45
M41e2
H2CO ppb
M41b6
40
M41c4
35
30
25
20
0 1 2 3 4 5 6 7
Days Conditioned
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Sampling and Analysis of Formaldehyde Emissions
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300
PB42-B9
250
PB42-C7/C8
PB42-A7/A8
200 PB42-C9
PB42-A9
PB42-C5/C6
PPB H2CO
PB42-B7/B8
PB42-A5/A6
150 PB42-A3/A4
PB42-B5/B6
PB42-B3/B4
PB42-C3/C4
100
50 PB42-C1/C2
PB42-A1/A2
PB42-B1/B2
0
1 2 3 7
Day
300
PB43-C7/C8
250 PB43-B9
PB43-C9
PB43-A7/A8
200
PPB H2CO
PB43-A9
PB43-C5/C6
PB43-B7/B8
150 PB43-B5/B6
PB43-A5/A6
PB43-A3/A4
PB43-B3/B4
100
PB43-C3/C4
50
PB43-A1/A2
PB43-C1/C2
PB43-B1/B2
0
1 2 3 7
Day
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Sampling and Analysis of Formaldehyde Emissions
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300
PB44-A9
PB44-B9
250
PB44-A7/A8
200
PB44-C9
PPB H2CO
PB44-C7/C8
PB44-C5/C6
150 PB44-B3/B4
PB44-A3/A4
PB44-C3/C4
PB44-B5/B6
100 PB44-B7/B8
PB44-A5/A6
PB44-C1/C2
50
PB44-A1/A2
PB44-B1/B2
0
1 2 3
Day
250
PB45-B9
PB45-A9
PB45-C9
200
PB45-A7/A8
PB45-C7/C8
PB45-C5/C6
PB45-B7/B8
150
PPB H2CO
PB45-C3/C4
PB45-B3/B4
PB45-B5/B6
PB45-A3/A4
PB45-C1/C2PB45-A1/A2
100 PB45-A5/A6
PB45-B1/B2
50
0
1 2 3 7
Day
NLB
170
PB36
160
150
M35
140
H2CO ppb
130
120
110
100
90
80
1/29/09
2/18/09
3/10/09
3/30/09
4/19/09
5/9/09
5/29/09
6/18/09
7/8/09
7/28/09
8/17/09
9/6/09
9/26/09
Date of Analysis