|
3M FORMALDEHYDE MONITOR (MODEL 3721)
| Classification: |
Product Evaluation (PE-10) (Backup Data Report for OSHA Method ID-205) |
| |
| Date: |
July, 1989 |
| |
| Authors: |
James Ku(1), Ed Zimowski(2), CIH |
Commercial manufacturers and products mentioned below are for
descriptive use only and do not constitute endorsements by USDOL-OSHA.
Health Response Team and the Branch of Inorganic Methods Development
OSHA Technical Center
Salt Lake City, Utah
Introduction
A field and laboratory evaluation of the 3M model 3721 formaldehyde monitor
was conducted by the OSHA Health Response Team (OSHA-HRT) and the OSHA
Analytical Laboratory. The model 3721 monitor had not, to our knowledge,
been thoroughly tested at the time of our evaluations (Field Study - 1986,
Lab Study - 1987-88). A preliminary study (9.1.) had been performed using a
model 3721 prototype; however, a different sampling rate than what is now
recommended was used for calculations.
Previous studies (9.1.-9.3.) of formaldehyde passive sampling and analysis
were conducted with the model 3751 monitor. The OSHA permissible exposure
limit (PEL) was a 3-ppm time weighted average (TWA) at the time of these
studies. The model 3751 monitor was replaced by 3M with the model 3721
monitor. Design changes introduced in the new monitor are Section 1. The OSHA
PELs for formaldehyde were changed in are summarized:
| Previous Standards |
Adopted Standards |
| 3 ppm TWA |
1 ppm TWA |
| 5 ppm Ceiling |
2 ppm STEL* |
| 10 ppm Peak |
---------- |
| *STEL = Short-Term Exposure Limit |
These changes signaled a need to re-examine the performance of this monitor.
This re-examination was accomplished using two studies:
Field Study: Samples were collected by the OSHA-HRT at various wood
products industries. Side-by-side samples were taken at field sites to
compare the 3M sampling and analytical method (9.5., 9.6.) with OSHA method
no. 52 (9.7.) and to determine occupational exposure to formaldehyde in wood
products manufacturing. Personal and area samples were taken. The
manufacturing processes sampled included assembly of particleboard, medium
density fiberboard, hardwood and softwood plywood, and paneling.
Lab Study: This portion of the product evaluation was conducted at the
OSHA Laboratory to determine if the re-designed 3M monitor is capable of
sampling accurately and precisely at different humidity and concentration
levels.
1. History
The simplicity and freedom of the 3M formaldehyde passive monitor (model 3751)
showed promise when first offered in 1981 as an industrial hygiene
sampling alternative for formaldehyde (9.8.); however, subsequent
independent studies indicated analyte loss when sampling at low humidities
(9.1., 9.3.). Consequently, the model 3751 monitor was removed from the
market by 3M in April, 1984. The model 3721 3M monitor, capable of sample
humidification, was introduced in 1985 as a replacement. The changes
instituted by 3M and incorporated into the model 3721 are:
- A water saturated pad in the bottom section of the monitor has been
added for sample humidification.
- Each monitor is now packaged in a sealed metal container. Previously,
the model 3751 monitor was enclosed in a resealable plastic bag.
- The calculated sampling rate has been changed from 0.0659 liters per
minute (L/min) to 0.0614 L/min*.
| * Note: |
The sampling rate of 0.0614 L/min is in agreement with a previous OSHA Laboratory study (9.2.). |
With the exception of the moisturizing pad, the model 3721 appears
physically identical to the model 3751 monitor.
The model 3751 monitor has been extensively evaluated by independent
laboratories (9.1.-9.3.). Results from these studies did not indicate
serious problems with desorption efficiency, face velocity, reverse
diffusion, or post-collection sample storage stability. The recent
modifications instituted by 3M do not suggest sampling performance would
be significantly affected in these areas. As long as the face velocity of
the sampled environment is above 3.1 to 4.6 m/min (10 to 15 ft/min), the
sampling rate of the monitor does not appear to be significantly altered
(9.1.-9.3. , 9.9.).
Sampling and analytical procedures are identical for either model
monitor; however, result calculations are different since slightly
different sampling rates are used.
2. Principle of the 3M Monitor
The 3M formaldehyde monitor is a diffusion-type air monitoring assembly.
The monitor is worn in the breathing zone of personnel in order to
evaluate potential exposure to formaldehyde vapors contained in the
atmosphere. The formaldehyde vapor passes through a diffusion barrier and
is adsorbed on bisulfite-impregnated paper contained within the monitor.
The formaldehyde collected by the monitor is laboratory analyzed by
desorbing the formaldehyde-bisulfite adduct from the treated paper with
formaldehyde-free deionized water. Chromotropic acid and sulfuric acid
are added to an aliquot of the sample to form a purple mono-cationic
chromogen. The absorbance of this colored solution is read in a
spectrophotometer at 580 nm and is proportional to the amount of
formaldehyde collected.
3. Evaluation Criteria
Field Study: The monitor lot numbers used during the field study were
unavailable. All monitors were tested before their expiration dates. The
field experiments involved taking side-by-side personal and area samples
with 3M monitors and treated XAD-2 solid sorbent contained in glass tubes.
These sampling tubes are further described in reference 9.7.
Personnel and area samples were taken in various occupational
environments where exposures to formaldehyde were near 1 ppm as a TWA.
Exposure levels were estimated using short-term detector tubes. A
portable, gas-phase infrared analyzer was used during the beginning of the
study to estimate exposures but was soon discontinued due to difficulties
with positive interferences. The wavelength recommended for analyzing
formaldehyde with the infrared analyzer measures C-H band stretching.
Other organic compounds in the sampled air tended to provide a positive
interference at this wavelength.
Results for the 3M monitor were compared to the treated XAD-2 sampling
device using linear regression statistics.
Lab Study: The laboratory experiments were mainly concerned with:
- Comparing the performance of the monitors near the 1 ppm PEL with a reference method
- Assessing performance in a low humidity environment (<50% RH)
- Taking STEL measurements (approximately 2 ppm for 15 min)
The 3M sampling and analytical method (9.5., 9.6.) was compared side-by-side
at the OSHA Laboratory to OSHA method no. ID-102 (9.10., 9.11.).
This method uses 10% methanol in midget fritted glass bubblers (MFGB) as
the sampling device.
Monitors obtained from 3M for the lab portion of the evaluation were
from lots 6125 002 (exp. date 10/20/87) and 8092 001 (exp. date 10/6/89).
All monitors were exposed and analyzed in the lab before their expiration
dates. The former lot was tested about 1 week before the expiration date.
(Note: A previous study (9.3.) of the 3751 monitor uncovered a shelf-life
problem where the bisulfite-treated pad appeared to dehydrate before the
expiration date. If the monitors were not used soon after manufacture,
the impregnated pad would not capture formaldehyde effectively in the
dehydrated state.)
Monitor performance was determined using formaldehyde test atmosphere
concentrations of approximately 0.4, 1, 1.5, 3, and 5 × PEL and calculated
using the OSHA Laboratory Inorganic Method Statistical Evaluation Protocol
(9.12.). Testing was mainly conducted for time-weighted average (TWA)
determinations. One experiment to determine the ability of the monitor to
sample STEL exposures was also performed at 50% RH. Lot 6125 002 was used
for experiments at 1.5, 3, and 5 × PEL while the other lot was used for
the remaining concentrations and the STEL experiment. Three different
RH levels (30, 50, and 80% RH) were used for each TWA concentration
tested. One exception is a test performed at 30% RH and 0.25 × PEL. This
concentration was used instead of 0.4 × PEL to evaluate monitor
performance under "worst case" conditions (low humidity - low concentration).
In addition, a separate experiment was conducted at the OSHA Laboratory
comparing the Field Study reference method with the Lab Study reference
method. This experiment was conducted by taking side-by-side treated
XAD-2 sorbent and 10% methanol MFGB samples at 50% RH and again at 80% RH.
All bubbler, tube, and monitor samples collected for the Field or Lab
Studies were analyzed at the OSHA Lab. All monitor samples were analyzed
according to the analytical procedure provided by 3M (9.6.).
4. Formaldehyde Test Atmospheres
Field Study: The formaldehyde concentration of samples taken in different
wood products industries was dependent on the type of adhesive or resin
mixture used, amount of production, and press temperature. The source of
exposure was mainly from either urea-formaldehyde (UF) or phenol-formaldehyde (PF)
resins with the former source predominating in the areas sampled. A variety of industrial
operations were sampled and the largest exposures to formaldehyde were confined to areas near
wood-pressing operations. The hot presses used to press the various woods together were
heated to temperatures ranging from 250 to 450 °F. The formaldehyde
concentration in any specific area near the presses varied according to
the press operation. When the press was closed and the wood/resin was
being heated, the concentration was low; the formaldehyde concentration
would increase when the press was opened. Therefore, most formaldehyde
concentrations at the field sites were not constant throughout the
sampling periods and fluctuated with press operation.
Lab Study: The apparatus used to generate dynamic test atmospheres of
formaldehyde for lab tests is shown as a block diagram in Figure 1. The
system consisted of five essential elements:
- A vapor generating chamber (permeation oven)
- A humidity control system
- A mixing manifold
- An aluminum passive monitor exposure channel
- A sampling manifold for active samplers
The formaldehyde was generated using permeation tubes containing reagent
grade paraformaldehyde. The permeation device used for generation of
formaldehyde vapor was a model 450 Dynacalibrator (VICI/Metronics, Santa
Clara, CA). The permeation device chamber was maintained at a constant
temperature of 110 °C. Concentrations of formaldehyde in the generation
system were preliminarily determined by the weight change of the
permeation tube. Weight changes are shown below:
Time Elapsed (min) |
Weight Loss (µg)
| Permeation Rate (µg/min)
|
| |
| 3,975 |
215,100 |
54.11 |
| 8,605 |
468,900 |
54.49 |
| |
| Average 54.30 ± 0.27 µg/min |
Purified air for contaminant dilution was prepared by flowing
compressed air through a particulate filter, a silica gel bed, and a
charcoal bed. Humidified air for dilution was produced by flowing the
purified air into a flow, temperature, and humidity control system
(Miller-Nelson Research Inc., model HCS-301).
A controlled formaldehyde concentration was produced by taking filtered
room air and passing it over the permeation tube, and then mixing with
the temperature-controlled (20 to 25 °C) humidified
air in a glass mixing manifold.
The contaminant-air mixture then entered a Teflon sampling manifold and
eventually a calibrated dry test meter (Singer Co., model no. DTM 115) for
flow rate measurement. The flow rate of the formaldehyde vapor to the
mixing chamber was approximately 0.17 L/min. Depending on the final
concentration desired, the flow rate range for dilution air was 5 to 25 L/min.
An aluminum exposure channel containing six openings, obtained from 3M
and also used in a previous OSHA study (9.2.), was connected to an arm of
the sampling manifold. This channel, as shown in Figure 2, was used to
test 5 monitors per experiment. The sixth port was sealed using an empty
monitor.
Monitor results were compared to the reference method sample results to
determine recovery ratios. The bias and overall error in a previous study
of the reference method (9.10., 9.11.) were +2.9% and ±19% respectively.
Theoretical results using the weight change of permeation tubes were not
used in the statistical analysis due to a small leak that developed in the
generation system during low concentration testing (tests done at <1 ×
PEL) . This leakage altered the actual generated concentration and
apparently was a result of the increased dilution volume necessary for low
concentration testing.
5. Sampling
Field Study: The field sampling technique provided by 3M (9.5.) was used
for taking monitor samples. Full shift samples were taken. Tubes
containing XAD-2 treated with 2-(hydroxymethyl) piperidine were
taken with Du Pent P125 sampling pumps at a flow rate of approximately 0.050 L/min.
For personal measurements, a monitor and a treated XAD-2 sampling device
were placed within 2 inches of each other on the lapel of the worker's
clothing. Area samples were placed in strategic areas near the operation
with each paired monitor and tube sample also being within 2 inches of
each other. Samples were sealed after sampling and submitted to the
OSHA Lab for analysis.
Lab Study: The monitor and reference samples were exposed using the
following step-by-step procedure:
- Adjust diluent flow rates in the dynamic generation system to
determine an approximate generated HCHO concentration. Adjust the
system to deliver either 30, 50, or 80% RH.
- Record the sample number and the exposure start time on the back of
each monitor.
- Before exposing, wrap parafilm around the edge of each monitor to
prevent leakage between each monitor and the exposure channel.
- For the reference samples, calibrate personal sampling pumps to
approximately 0.5 L/min sampling rates. Add approximately 15 mL of
10% methanol (MeOH) to midget fritted glass bubblers (MFGB).
- Place the monitors in the exposure channel and attach MFGBs to the
sampling manifold. Simultaneously expose the bubblers and the monitors.
- At the conclusion of the sampling period, immediately remove and
discard the white plastic film and purple retaining ring from the top
of the monitor. Also remove the bottom portion which contains the
metal clip.
- Firmly snap the closure caps onto the monitor faces.
- Place the MFGB solutions into 25-mL volumetric flasks and dilute to
the mark with 10% MeOH. Post-calibrate the sampling pumps.
- Record the exposure end time on the back of the monitor.
- Enclose the monitor in the original aluminum container until ready for
analysis.
This procedure (a to j) was repeated for each humidity-concentration level
tested.
As previously mentioned, reference MFGB samples were taken according
the procedures outlined in references 9.10 and 9.11. The MFGB sampling
times for the TWA determinations varied between 30 and 240 min. Six MFGB
and five monitor samples were tested at each concentration/humidity level.
All monitor samples were exposed for 240 min except for the STEL
experiment which took 15 min.
The exposure channel inlet was connected to the manifold and the outlet
was connected to a Du Pont P4000 sampling pump whose sampling rate was set
at 3 to 5 L/min. This flow range produced face velocities inside the
channel of 9.2 to 15.3 m/min (30 to 50 ft/min). As shown in Figure 2, the
monitor samples are placed in series in the channel such that the
formaldehyde mixture contacts the first and then subsequent monitors. If
the flow rate through the channel is less than 6 L/min, a "starvation
effect" is produced from one monitor to another. The flow rates in this
3M sampling chamber were less than 6 L/min and all results were corrected
for this "starvation" using the following equation (9.9.):
| Cn = |
Co × [FR - (n - 1) SR] FR |
Where:
| Cn |
= |
HCHO theoretical concn (in ppm) as sampled by the nth sampler |
| Co |
= |
HCHO (in ppm) in the generation system |
| FR |
= |
Air flow rate in the sampling chamber |
| SR |
= |
Diffusional sampling rate for the contaminant (0.0614 L/min) |
| n |
= |
Placement in the channel; the monitor first exposed to the
formaldehyde mixture would have a value of n = 1, and n = 5 for the
last monitor exposed in the channel. |
6. Analysis
Field and Lab Studies - 3M Monitors: The analytical procedure used was
the NIOSH P&CAM 125 procedure for analysis of formaldehyde (9.13.) which
has been slightly modified by 3M. Modifications were apparently
instituted to alter the analytical working range and minimize
interferences. These modifications include:
- A smaller total sample volume (3 mL) and greater sample/aliquot ratio (3/2) are used.
- A change from a ratio of 4.0: 0.1: 6.0 mL (NIOSH method) to
2.0: 1.0: 5.0 mL (3M monitor method) for the analytical reagents
listed below.
sample: 1% chromotropic acid: concentrated sulfuric acid
The formaldehyde adsorbed on the bisulfite-impregnated adsorbent was
analyzed according to the procedure described below (9.6.):
- The formaldehyde-bisulfite adduct was desorbed by adding 3 mL of
deionized water (DI H2O) through the center port of the elutriation
cap (outer cap) using a pipette. The port was re-sealed.
- The sample was allowed to sit for 30 min with occasional gentle
agitation. A 2-mL aliquot of the solution was then transferred into a
20-mL screw-cap glass vial.
- A purple color was produced in this aliquot after addition of 1 mL of
1% chromotropic acid solution along with slow and careful addition of
5 mL concentrated sulfuric acid. This mixture was agitated and then
allowed to cool to room temperature.
- The absorbance was measured with a UV-VIS Model Spectronic 100 single
beam spectrophotometer (Bausch & Lomb, Rochester, NY) or a double beam
CARY 219 UV-VIS spectrophotometer (Varian Associates, Palo Alto, CA)
at 580 nm using a 1-cm cell.
Field Study - Solid sorbent samples: The resulting derivative
[formaldehyde plus 2-(hydroxymethyl) piperidine] was desorbed from the
XAD-2 treated sorbent with toluene and then nitrogen selective detector as specified in
reference 9.7.
Lab Study (MFGB samples): The 10% MeOH solutions were buffered,
hydrazine was added, and the resulting hydrazone compound was analyzed by
square wave polarography. This technique was used instead of the
differential pulse polarographic technique mentioned in reference 9.10.
and 9.11. because it offered a decrease in analysis time with comparable
results.
7. Results
The weight of formaldehyde collected by each monitor was calculated
a polynomial regression concentration-response curve. Samples were
using blank corrected and the average concentration of formaldehyde in the sampled
ambient air was then calculated by (9.6.):
|
| C = |
W × MV t × K × RC × MW |
|
(1) |
Where:
|
C |
= |
Average formaldehyde concentration (ppm) |
|
W |
= |
Weight (from curve, as µg) |
|
MV |
= |
Molar volume (at 25 °C and 760 mmHg, MV = 24.45 L/mole) |
|
MW |
= |
Molecular weight of formaldehyde (30 g/mole) |
|
K |
= |
Monitor sampling rate for formaldehyde (0.0614 L/min) |
|
RC |
= |
Recovery coefficient for formaldehyde |
|
t |
= |
Length of sampling period (min) |
Since RC = 1.00 (9.2., 9.6.), equation (1) was simplified to:
Sample results for solid sorbent and bubbler samples were calculated
according to their respective methods (9.7., 9.10.) The results of the
experiments can be found in these Tables:
Experiment
|
|
Table
|
| 3M monitors vs. Treated XAD-2 (Field Study) |
|
|
1 (also Figure 3) |
| 3M monitors - 240 min samples (Lab Study) |
|
|
2 |
| 3M monitors - STEL experiment (Lab Study) |
|
|
3 |
| 3M monitors - Summary (Lab Study) |
|
|
4 (also Figure 4) |
| Treated XAD-2 vs. MFGB Samplers |
|
|
5 |
Field Study: Shown below are the results from linear regression plotting
of the data shown in Table 1 and Figure 3:
Linear Regression
(XAD-2 Treated Tube vs. 3M Monitor)
| Correlation coefficient |
(r) = |
0.976 |
| Intercept |
(a) = |
-0.0059 |
| Slope |
(b) = |
0.952 |
| Standard deviation of slope |
(Sb) = |
0.037 |
When comparing two different methods by linear regression, ideal agreement
between methods is displayed if the correlation coefficient and the slope
are equal to a value of 1. As shown in Figure 3, the dashed line
corresponding to ideal agreement does not differ greatly from the
regression line calculated from field results. When considering the slope
and the standard deviation of the slope at 95% confidence
(0.952 ± 2 × 0.037), the slope does not significantly differ from a value
of 1. The correlation coefficient is also close to 1. Therefore, the 3M
and XAD-2 sampling media gave similar results throughout the concentration
range tested at the field sites. Both sampling devices also gave similar
results regardless of the workplace source for formaldehyde or industrial
operation.
Average blank values for monitors analyzed during the Field Study were
approximately 1 µg.
Lab Study: Table 2 contains individual monitor results for the three RH
levels and five concentrations tested. A positive bias is noted when
comparing monitors with MFGBs. As previously mentioned, generation system
leakage at low concentrations prevented theoretical results from being
used and therefore, monitor results were only compared with MFGB results.
Theoretical results at generated concentrations greater than the PEL were
available and a comparison with monitor results gave an acceptable overall
error (9.12.) of ±21.7%. When comparing the monitor and MFGB recoveries
using theoretical values in this concentration range, the MFGB average
recovery was 8.7% less than the monitors.
Table 3 contains results for the five monitors taken at the STEL. The
STEL measurements indicate somewhat variable results are obtained when
sampling for a short duration.
Table 4 contains a summary of Table 2 data and F test results. As
shown in Table 4, the monitor displayed a total recovery ratio of 1.064
and thus, a positive overall bias of 6.4%. Figure 4 graphically displays
the comparison of recovery ratios for the monitor and MFGB samples. Each
point on the graph is an average of five or six sample recovery ratios at
a given concentration and RH. In this Figure, ideal agreement between the
two methods is shown by the dashed line. Bias is displayed when the solid
line (slope of actual measurements) moves towards either axis. Positive
bias is shown by the solid line leaning toward the 3M axis.
An F test was used to detect any significant variability in results
across the three humidity levels tested. The F test monitor results in
Table 4 show a significant difference does exist at the 99% confidence
level. An examination of recovery ratios at the different RH levels
(Table 2) indicates an enhancement at 80% RH. Recovery ratios were
approximately 10% higher at 80% RH. A shift in performance due to
humidity was not noted for the reference method.
Blank values for monitors analyzed during the Lab Study ranged from
0.91 to 3.39 µg with a CV of 0.55. If the 3.39 µg measurement is omitted,
the blank values are much closer with a range of 0.91 to 1.5 µg and a CV
of 0.21.
The comparison of the treated XAD-2 sampling device with MFGBs showed
agreement between the two methods (Table 5). A slight positive bias of
the XAD-2 device over the MFGB is also shown. This bias tended to
increase with increasing RH.
8. Summary
The 3M model 3721 monitor and selected reference methods gave similar
formaldehyde results in field and lab experiments when samples were taken
for at least 240 min. The field study indicates the monitor results were
not significantly different from the treated XAD-2 sampling device. A
positive bias was noted when the monitor was compared in the Lab Study to
the 10% methanol sampling device; however, this bias can be accounted for
since the MFGB method appears to be giving results approximately 5 to 10%
lower than either the monitor or the treated XAD-2 sampling device. At
high humidity (80% RH), tests in the laboratory indicated the monitor gave
a slight positive bias when compared to the MFGBs.
Short-term sampling with the monitor may give highly variable results.
This variability could be due to insufficient equilibration time or to the
decreased amount of analyte taken. The time necessary to passivate the
surfaces of the monitor and to achieve a homogeneous sampling rate may be
longer than 15 min. Any analytical method has difficulty when measuring
amounts of analyte near the method's detection limit. The total amount of
formaldehyde generated at the STEL was approximately 2 µg. This amount is
near the analytical detection limit described by 3M (9.9.). Even if this
amount is detectable using the procedure described, the blank values noted
in the Lab Study were approximately 1 to 3 µg. If the blank value is
not consistent, the measurement of any sample near the blank value can
become erratic and inaccurate.
As previously mentioned, during the Field Study the concentration of
formaldehyde usually fluctuated over the sampling period. The variability
in concentration did not appear to affect the ability of the monitor to
sample. These results agree with a previous study (9.2) performed using
fluctuating formaldehyde concentrations under laboratory conditions.
Concentrations and humidities used to test the monitor were in the
range normally expected in workplace situations. Overall results indicate
the monitor gave similar results to the 10% methanol MFGBs and treated
XAD-2 sampling devices and is an alternative for formaldehyde TWA
sampling.
9. References
9.1. National Council of the Paper Industry for Air and Stream Improvement Inc.:
A Laboratory Evaluation on the Performance of Passive Diffusion Badge Monitors and
Detector Tubes for Determination of Formaldehyde. (Technical Bulletin No. 451),
NY: NCASI, 1985.
9.2. Occupational Safety and Health Administration Analytical Laboratory:
Evaluation of 3M Formaldehyde Monitors (Model 3751) by J.C. Ku
(USDOL/OSHA-SLCAL Product Evaluation no. ID-139). Salt Lake City, UT. 1982 (unpublised).
9.3. Kennedy, E.R. and R.D. Hull: Evaluation of the Du Pont Pro-Tek
Formaldehyde Badge and the 3M Formaldehyde Monitor. Amer. Ind. Hyg. Assoc. J. 47:94-105 (1986).
9.4. "Formaldehyde," Code of Federal Regulations Title 29, Pt. 1910,
Section 1048. 1988. pp. 992-1028.
9.5. Occupational Health and Safety Products Division/3M: 3M Formaldehyde
Monitor #3721 Instructions for Use. St. Paul, MN: 3M Company. No
publication date given.
9.6. Occupational Health and Safety Products Laboratory: Organic Vapor
Method no. 4D. St. Paul, MN: 3M Company, May, 1985.
9.7. Occupational Safety and Health Administration Analytical Laboratory:
OSHA Analytical Methods Manual (USDOL/OSHA-SLCAL Method No. 52).
Cincinnati, OH: American Conference of Governmental Industrial
Hygienists" (Pub. no. ISBN: 0-936712-66-X), 1985.
9.8. Rodriguez, S.T., P.B. Olson, and V.R. Lund: "Colorimetric Analysis
of Formaldehyde Collected on a Diffusional Monitor." Paper presented
at Amer. Ind. Hyg. Assoc. Conference, Portland, OR, May 1981.
9.9. Occupational Health and Safety Products Division/3M: 3M Brand
Formaldehyde Monitor #3750/3751. St. Paul, MN: 3M Company, Internal
document - No publication date given.
9.10. Occupational Safety and Health Administration Analytical Laboratory:
OSHA Analytical Methods Manual (USDOL/OSHA-SLCAL Method and Backup
Report no. ID-102). Cincinnati, OH: American Conference of
Governmental Industrial Hygienists (Pub. no. ISBN: 0-936712-66-X), 1985.
9.11. Septon, J.C. and J.C. Ku: Workplace Air Sampling and Polarographic
Determination of Formaldehyde. Amer. Ind. Hyg. Assoc. J. 43:845-852
(1982).
9.12. Occupational Safety and Health Administration Analytical Laboratory:
Precision and Accuracy Data Protocol for Laboratory Validations. In
The OSHA Laboratory Methods Manual. Cincinnati, OH: American
Conference of Governmental Industrial Hygienists (Pub No. ISBN:
0-936712-66-X), 1985.
9.13. National Institute of Occupational Safety and Health: NIOSH Manual
of Analytical Methods, 1st ed. (P&CAM 125) edited by D. Taylor
(DHHS/NIOSH Pub. 77-157-A). Cincinnati, OH: NIOSH, 1977.
Table 1Field Samples
| |
Company
|
Type
|
|
Operation
|
XAD-2 (ppm)
|
|
3M (ppm)
|
E E E E F F A A B D A
A E A A A C A H H A C H C E
G B F F F F F F B D |
|
Ar Ar Ar Ar P P P P P Ar P P Ar
P P P P P Ar Ar P Ar Ar P Ar Ar
P Ar Ar Ar Ar Ar Ar P Ar |
|
Press Operator Press Operator Press Unloader Press Unloader
Press Operator Press Operator Patcher Core Feeder
On Walkway Above Conveyer (mat former) Strip Stacker Production Saw
Patcher Big Dry Chain Grader Top of Press Dry End Fork Lift
Core Feeder Little Dry Chain Grader Utility Big Dryer Feeder
Style Grain Topcoat Operator Topcoat Operator Small Dryer Feeder
Adjacent to Cooling Wheel Laminating Line - Topcoat Operator
Cleanup Top of Press - Glue Mixing Press Operator
On Walkway above Conveyer to Hot Press Top of Press Top of Press
Top of Press Top of Press Top of Press Top of Press
Above Conveyer Top of Press |
0.12 0.12 0.12 0.15 0.11 0.13
0.21 0.26 0.27 0.21 0.28 0.22 0.26 0.26
0.30 0.26 0.38 0.18 0.43 0.52 0.25 0.60
0.43 0.52 0.69 0.78 1.12 0.90 0.99 1.14
0.17 1.28 1.26 2.12 2.42 |
|
0.082 0.084 0.092 0.10 0.14 0.13 0.20
0.21 0.22 0.22 0.23 0.24 0.24 0.27
0.28 0.30 0.30 0.28 0.35 0.35 0.36
0.44 0.44 0.57 0.60 0.81 0.93 0.97
1.35 1.16 1.06 1.06 1.26 1.90 2.42 |
A = Softwood plywood plant using phenol-HCHO (PF) adhesive
B = Particleboard plant (highly automated) using urea-HCHO (UF) adhesive
C = Particleboard plant using UF resin
D = Particleboard plant using UF resin
E = Hardwood plywood plant using UF resin
F = Hardwood plywood plant using UF resin
G = Medium density fiberboard plant using UF resin
H = Hardwood paneling plant using topcoat of UF resin
Ar = Area Sample P = Personal Sample
Table 2
Precision and Accuracy
for
3M Formaldehyde Monitors (Model 3721)
(a) 30% RH & 25 °C
|
HCHO Concn* (ppm) |
HCHO Found (ppm) |
Statistical Analysis
|
|
| 0.247 |
0.253 |
n |
= 5 |
|
0.270 |
Mean (ppm) |
= 0.242 |
|
0.241 |
Std Dev (ppm) |
= 0.021 |
|
0.221 |
CV |
= 0.086 |
|
0.223 |
Recovery Ratio |
= 0.978 |
| |
| 1.07 |
0.852 |
n |
= 5 |
|
1.01 |
Mean (ppm) |
= 0.959 |
|
0.887 |
Std Dev (ppm) |
= 0.092 |
|
0.968 |
CV |
= 0.096 |
|
1.08 |
Recovery Ratio |
= 0.896 |
| |
| 1.61 |
1.63 |
n |
= 5 |
|
1.53 |
Mean (ppm) |
= 1.61 |
|
1.70 |
Std Dev (ppm) |
= 0.062 |
|
1.60 |
CV |
= 0.039 |
|
1.59 |
Recovery Ratio |
= 1.000 |
| |
| 2.87 |
3.45 |
n |
= 5 |
|
3.34 |
Mean (ppm) |
= 3.27 |
|
3.13 |
Std Dev (ppm) |
= 0.12 |
|
3.23 |
CV |
= 0.038 |
|
3.22 |
Recovery Ratio |
= 1.139 |
| |
| 4.48 |
5.01 |
n |
= 5 |
|
4.64 |
Mean (ppm) |
= 5.31 |
|
5.46 |
Std Dev (ppm) |
= 0.48 |
|
5.64 |
CV |
= 0.090 |
|
5.81 |
Recovery Ratio |
= 1.185 |
| |
All concentration levels (30% RH)
Recovery Ratio = 1.040
CV(pooled) = 0.075 |
| |
|
|
* Values from average recovery of six MFGB samples analyzed by polarography |
|
Precision and Accuracy
for
3M Formaldehyde Monitors (Model 3721)
(b) 50% RH & 25 °C |
|
HCHO Concn* (ppm) |
HCHO Found (ppm) |
Statistical Analysis
|
|
| 0.414 |
0.438 |
n |
= 5 |
|
0.418 |
Mean (ppm) |
= 0.418 |
|
0.436 |
Std Dev (ppm) |
= 0.020 |
|
0.391 |
CV |
= 0.047 |
|
0.407 |
Recovery Ratio |
= 1.01 |
| |
| 1.15 |
1.13 |
n |
= 5 |
|
1.15 |
Mean (ppm) |
= 1.10 |
|
1.09 |
Std Dev (ppm) |
= 0.038 |
|
1.06 |
CV |
= 0.035 |
|
1.08 |
Recovery Ratio |
= 0.958 |
| |
| 1.41 |
1.47 |
n |
= 5 |
|
1.58 |
Mean (ppm) |
= 1.52 |
|
1.57 |
Std Dev (ppm) |
= 0.063 |
|
1.55 |
CV |
= 0.041 |
|
1.44 |
Recovery Ratio |
= 1.078 |
| |
| 2.88 |
3.03 |
n |
= 5 |
|
3.44 |
Mean (ppm) |
= 2.78 |
|
2.72 |
Std Dev (ppm) |
= 0.47 |
|
2.40 |
CV |
= 0.169 |
|
2.30 |
Recovery Ratio |
= 0.965 |
| |
| 4.91 |
5.34 |
n |
= 5 |
|
5.62 |
Mean (ppm) |
= 5.30 |
|
5.22 |
Std Dev (ppm) |
= 0.19 |
|
5.13 |
CV |
= 0.036 |
|
5.21 |
Recovery Ratio |
= 1.079 |
| |
All concentration levels (50% RH)
Recovery Ratio = 1.018
CV(pooled) = 0.084 |
| |
|
| * Values from average recovery of six MFGB samples analyzed by polarography |
|
Precision and Accuracy
for
3M Formaldehyde Monitors (Model 3721)
(c) 80% RH & 25 °C |
|
HCHO Concn* (ppm) |
HCHO Found (ppm) |
Statistical Analysis
|
|
| 0.460 |
0.533 |
n |
= 5 |
|
0.568 |
Mean (ppm) |
= 0.502 |
|
0.474 |
Std Dev (ppm) |
= 0.048 |
|
0.448 |
CV |
= 0.096 |
|
0.485 |
Recovery Ratio |
= 1.090 |
| |
| 0.910 |
1.04 |
n |
= 3 |
|
0.975 |
Mean (ppm) |
= 0.991 |
|
0.202** |
Std Dev (ppm) |
= 0.043 |
|
0.959 |
CV |
= 0.043 |
|
0.728** |
Recovery Ratio |
= 1.089 |
| |
| 1.47 |
1.69 |
n |
= 5 |
|
1.77 |
Mean (ppm) |
= 1.79 |
|
1.84 |
Std Dev (ppm) |
= 0.072 |
|
1.88 |
CV |
= 0.040 |
|
1.79 |
Recovery Ratio |
= 1.218 |
| |
| 2.91 |
2.83 |
n |
= 5 |
|
3.37 |
Mean (ppm) |
= 3.20 |
|
3.07 |
Std Dev (ppm) |
= 0.26 |
|
3.26 |
CV |
= 0.080 |
|
3.48 |
Recovery Ratio |
= 1.100 |
| |
| 4.62 |
5.28 |
n |
= 5 |
|
5.71 |
Mean (ppm) |
= 5.44 |
|
5.55 |
Std Dev (ppm) |
= 0.18 |
|
5.36 |
CV |
= 0.033 |
|
5.32 |
Recovery Ratio |
= 1.177 |
| |
All concentration levels (80% RH)
Recovery Ratio = 1.139
CV(pooled) = 0.065 |
| |
|
| * Values from average recovery of six MFGB samples analyzed by polarography |
| ** Not included in statistical analysis - considered outliers |
|
Table 3
Precision and Accuracy
for
3M Formaldehyde Monitors (3721)
50% RH & 25 °C - STEL Determination
|
HCHO Concn* (ppm) |
HCHO Found (ppm) |
Statistical Analysis
|
|
| 2.22 |
3.02 |
n |
= 5 |
|
1.68 |
Mean (ppm) |
= 1.91 |
|
0.975 |
Std Dev (ppm) |
= 0.737 |
|
2.03 |
CV |
= 0.385 |
|
1.87 |
Recovery Ratio |
= 0.86 |
|
| * Values from average recovery of six MFGB samples analyzed by polarography |
Table 4
Summary of Lab Recoveries Pooled across 3 RH levels
|
| Level |
CVT |
Recovery Ratio |
|
|
| Below 1 × PEL |
0.079 |
1.026 |
| 1 × PEL |
0.069 |
0.982 |
| 1.5 × PEL |
0.040 |
1.099 |
| 3 × PEL |
0.11 |
1.068 |
| 5 × PEL |
0.059 |
1.147 |
|
Pooled Summarv of All Concentration and RH Levels
|
| Recovery Ratio(total) = 1.064 |
CV(pooled) = 0.075 |
| |
| At the 99% confidence level: |
| Fcrit (3M) |
= 4.92 |
Fcalc (3M) |
= 9.0 |
(2, 70 degrees of freedom) |
| Fcrit (MFGB) |
= 5.06 |
Fcalc (MFGB) |
= 0.51 |
(2, 50 degrees of freedom*) |
| |
| For the 3M monitors: Fcrit < Fcalc; therefore, a significant difference in
results exists across the three RH levels tested. |
| |
| For the MFGB: Fcrit > Fcalc; therefore, a significant difference in results
was not noted across the three humidity levels tested. |
|
| * Only results > 1 ppm were used. |
Table 5
Comparison of Methods
XAD-2 vs. 10% MeOH
(a) 50% RH and 25 °C
|
| Sample No. |
XAD-2 ppm |
10% MeOH ppm |
XAD-2/10% MeOH |
|
|
1 |
0.870 |
0.849 |
|
2 |
0.853 |
0.835 |
|
3 |
0.885 |
0.838 |
|
4 |
0.862 |
0.814 |
|
5 |
|
0.827 |
| |
|
n |
= 4 |
5 |
|
Mean |
= 0.868 |
0.833 |
1.04 |
|
Std Dev |
= 0.014 |
0.013 |
|
CV |
= 0.016 |
0.016 |
|
|
(b) 80% RH and 25 °C
|
|
|
| Sample No. |
XAD-2 ppm |
10% MeOH ppm |
XAD-2/10% MeOH |
|
|
1 |
1.03 |
0.891 |
|
2 |
0.941 |
0.890 |
|
3 |
1.01 |
0.917 |
|
4 |
1.01 |
0.934 |
|
5 |
|
0.916 |
| |
|
n |
= 4 |
5 |
|
Mean |
= 0.998 |
0.910 |
1.10 |
|
Std Dev |
= 0.039 |
0.019 |
|
CV |
= 0.039 |
0.021 |
|
Block Diagram of the Major components in a Dynamic Generation System
Figure 1
3M Monitor Aluminum Exposure Channel
| Note: |
The square sampling ports are shown to illustrate sample placement.
The Ports are round on the actual channel. |
Figure 2
Field Study
Figure 3
Lab Study
Figure 4
Footnote (1) Research Chemist, Branch of Inorganic Methods Development, OSHA Technical
Center, Salt Lake City, UT.
Footnote (2) Senior Industrial Hygienist, Health Response Team, OSHA Technical Center.
(Back to top)
|