IOH-RS-BR-SR-2005-0005

UNITED STATES AIR FORCE

AFIOH

Estimating Organic Vapor

Cartridge Service Life

David S. DeCamp, Captain, USAF, BSC

Joseph Costantino, Major, USAF, BSC
_Jon E. Black, Captain, USAF, BSC

20051114 021
November 2004

Air Force Institute for Operational Health

Risk Analysis Directorate
Approved for public release; Health and Safety Division
2513 Kennedy Circle
distributionis unlimited. Brooks City-Base TX 78235-5116
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r4

DAVID S. DECAMP DiVID R. CARPENTER

Industrial Hygiene Consultant Chief, Health and Safety Division
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I November 2004 FINAL

4. TITLE AND SUBTITLE 5. FUNDING NUMBERS
Estimating Organic Vapor Cartridge Service Life

6. AUTHOR(S)
DeCamp, David. S., Captain
Costantino, Joseph, Major
Black, Jon. E., Captain
7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION
Air Force Institute for Operational Health REPORT NUMBER
Risk Analysis Directorate IOH-RS-BR-SR-2005-0005
Health and Safety Division
2513 Kennedy Circle
Brooks City-Base. TX 78235-5116
9. SPONSORINGIMONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING/MONITORING
AGENCY REPORT NUMBER

11. SUPPLEMENTARY NOTES

12a. DISTRIBUTION AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE

Approved for public release; distribution is unlimited.

13. ABSTRACT (Maximum 200 words)

Respirator cartridge change-out schedules depend upon many factors such as the contaminant, airborne concentration,
humidity, temperature cartridge, and worker characteristics. End of service life indicator (ESLI) estimator calculators have
been created by several cartridge manufacturers including 3M, North, and MSA. This technical report details background
information pertaining to cartridge change-out schedules with regard to OSHA and Air Force requirements and manufacturer
calculators which may be used to establish cartridge change-out schedules.

14. SUBJECT TERMS 15. NUMBER OF PAGES

58
Respirator, Cartridge Change-Out, Cartridge Service Life, End of Service Life Indicator, 16. PRICE CODE
Breakthrough
17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRAC!
OF REPORT OF THIS PAGE OF ABSTRACT

Unclassified Unclassified Unclassified UL

Standard Form 298 (Rev. 2-89) (EG)
Prescribed by ANSI Std. 239.18
Designed using Perform Pro, WHS/DIOR, Oct 94
THIS PAGE INTENTIONALLY LEFT BLANK

ii
 Table of Contents

Introduction .............................................................................................. 1
Regulatory Drivers ..................................................................................... 2
P articulates ............................................................................................... 2
Chemicals not suited for OV Cartridges .............................................................. 2
Rules of Thumb .......................................................................................... 3
Experimental Testing ................................................................................... 3
Manufacturer's Data .................................................................................... 4
Mathematical Models .................................................................................. 4
M ixtures .................................................................................................. 5
Softw are ................................................................................................... 6
Lim itations ................................................................................................. 8
Some Considerations for Specific AF Jobs ........................................................... 8
References ............................................................................................... 10

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 List of Attachments

1. Estimating Cartridge Service Life Flowchart

2. Cartridge Service Life for OSHA Substance-Specific Standards
3. Field Testing of Cartridge Effectiveness for a Contaminant
4. Mask Sampling Adapters Available from U.S. Respirator Manufacturers
5. Respirator Manufacturers
6. Factors to Consider When Developing a Cartridge Change-out Schedule
7. Calculating the Wood Equation
8. Correction Factor versus Solvent Concentration at 85% Relative Humidity
9. The Wood Math Model Table at the OSHA website
10. OSHA's Example on How to use a Math Model Table
11. OSHA's Example on How to use a Math Model Equation
12. How to Calculate Service Life for Mixtures
13. Summary of Software Features
14. Chemical Selection for Cartridge Service Life per Manufacturer
15. Comparison of Software Programs Breakthrough Times
16. Estimated Cartridge Service Life for Cartridges Exposed to JP-8
17. Manufacturer Cartridge Properties

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Introduction

The service life of a cartridge is the period of time for which the cartridge provides adequate
protection to the user. After a cartridge has absorbed a particular contaminant to its capacity, the
contaminant will begin to pass through the cartridge and enter the facepiece of the respirator, a
condition commonly referred to as breakthrough. A cartridge change-out schedule allows the
respirator wearer to replace the chemical cartridge or canister before breakthrough occurs, instead
of relying on the contaminant's warning properties. An appropriate cartridge change schedule is
one that is both convenient and assures that the concentration of the chemical downstream does
not exceed the exposure limit. Attachment 1 shows a decision matrix flowchart for starting to
setup a change-out schedule.

User senses (odor, taste, irritation, etc.) are not acceptable means for determining cartridge
service life because warning properties rely upon human senses that are not foolproof. The 1987
NIOSH Respirator Decision Logic described the typical wide variation of odor threshold in the
general population (greater than two orders of magnitude). Other problems exist: shift in odor
threshold due to extended low exposures, shifts due to simple colds and other illnesses, and
failure to recognize odor due to distraction in the workplace competing for worker attention.
Given the variability among people with respect to detection of odors and differences in
measuring odor thresholds, a better practice is to establish cartridge change-out schedules even
for chemicals with adequate warning properties.

Certain cartridges are designed with the capability of warning the user when it is time to change
the cartridges. Currently, there are very few cartridges equipped with National Institute for
Occupational Safety and Health (NIOSH)-approved end-of-service life indicators (ESLIs).
ESLIs are available for exposures to mercury vapor, carbon monoxide, hydrogen sulfide, and
ethylene oxide. The small area at the center of the inlet surface of cartridges with ESLIs and the
band around the side of the cartridge consists of chemically treated paper. During use, as the
paper is exposed to the specific chemical, it changes from one color to another. When the
indicator color changes, the cartridge is beginning to lose its effectiveness against vapor or gas
and should be replaced. Thus, the wearer has a constant, positive check on the condition of this
cartridge.

Regulatory Drivers

The Occupational Safety and Health Administration (OSHA) standard 29 Code of Federal
Regulations (CFR) 1910.134(d)(3)(iii) states that for protection against gases and vapors,
employers shall provide either a respirator with an ESLI certified by NIOSH for the contaminant
or implement a change schedule for canisters and cartridges that is based on objective
information or data that will ensure that canisters and cartridges are changed before the end of
their service life.

Paragraph 4.2.2.10 of AFOSH Standard 48-137, Respiratory ProtectionProgram,states to use

air-purifying devices only if the air-purifying respirator has a reliable end of service life indicator
that will warn the user prior to contaminant breakthrough, or a cartridge change schedule is
implemented based on cartridge service data including desorption studies (unless cartridges are
changed daily); expected concentration; pattern of use; duration of exposure have been
established; and the chemical does not have a ceiling limit. If the latter is the case,
Bioenvironmental Engineering (BE) shall determine that the respirator will provide adequate
protection and the change schedule is appropriate.

Also, paragraph 7.3.6. of AFOSH Standard 48-137 requires initial respiratory protection training
to include an explanation of how a worker knows when to change the filters or cartridges on an
air-purifying respirator. Paragraph 9.3.3.4. requires workplace respiratory protection operating
instructions to include the criteria which workers use to determine when respirator filters,
cassettes, or cartridges must be changed. Notwithstanding, paragraph 8.4.2. states that the
cartridge, filter, or canister of an air-purifying respirator shall be changed:

(a) Whenever the worker detects an increase in breathing resistance;

(b) Whenever the worker smells or tastes the contaminant, or detects the irritant properties of
the contaminant;
(c) Whenever the ESLI is triggered;
(d) As required by applicable substance-specific OSHA standards (for instance,
formaldehyde); or
(e) As directed by BE.

For gas and vapor contaminants regulated by OSHA's substance-specific standards, minimum
cartridges change schedules are already specified (see Attachment 2).

Particulates

Service life determination for particulate filters is not required under 29 CFR 1910.134; it is only
required for gases and vapors. Normally, the particulate filtration efficiency will improve during
use as the filter loads and a "cake" layer forms on the surface of the filter. Respirators or filters
should be changed if they become damaged, soiled, or an increase in breathing resistance
becomes noticeable. In addition to these considerations, N series filters should not be used
against oily aerosols. The NIOSH 1996 Publication 96-101, Guide to the Selection and Use of
ParticulateRespirators,recommends that R series filters should be changed every 8 hours if
used against oily aerosols. Most manufacturers recommend that their P series filters used in
environments containing oily aerosols should be limited to 40 hours of use or 30 days, whichever
is first.

Chemicals not suited for OV Cartridges

Respirator organic vapor (OV) cartridge performance is particularly poor when removing
methanol, dichloromethane, carbon disulfide, methyl chloride, acetone, and methyl acetate. Due
to the short breakthrough times for these solvents, other adsorbents or collectors should be used.
To make the cartridges more selective for certain chemicals, sorbents can be impregnated with
chemical reagents. Impregnated activated carbon removes specific gas and vapor molecules by
chemisorption. Chemisorption is the formation of bonds between molecules of the impregnant

2
and the chemical contaminant. These bonds are much stronger than the attractive forces of
physical adsorption. The binding is usually irreversible. Reuse of chemical cartridges that work
on the principle of chemisorption typically not be a problem. Although counterintuitive, the
service life of acid gas, ammonia/methylamine, and other chemical cartridges that work by
chemisorption, typically increase with increasing relative humidity.

Rules of Thumb

As part of the overall assessment for determining a change-out schedule, one might look to
various "rules of thumb" that have appeared in published literature. Please note that these "rules
of thumb" do not work for every chemical in every situation (in particular, these statements do
not generally apply to inorganic gases such as sulfur dioxide and hydrogen sulfide):

(a) If a chemical's boiling point is greater than 70'C and the concentration is less than 200
ppm you can expect a service life of eight hours at a normal work rate;
(b) Service life is inversely proportional to work rate;
(c) Reducing concentration by a factor of ten will increase service life by a factor of five;
(d) Humidity above 85% will reduce service life by 50%;
(e) Breakthrough times are diminished from 1-10% with each 10TC rise in temperature; and
(f) Service life is directly proportional to the amount of carbon in the cartridge.

Since the "rules of thumb" are based on a few parameters such as concentration and boiling
point, they are considered subjective. To comply with the OSHA standard, objective data must
be used. There are three valid ways to estimate a cartridge's service life: conduct experimental
tests, use the manufacturer's recommendation, or use a mathematical model.

Use of Analogous Chemical Structures

Appendix A of CPL 2-0.120 states that analogous structures may be used as the basis for
estimating cartridge breakthrough where a contaminant with a known service life value has an
analogous structure to the contaminant under investigation or where a contaminant with a known
migration may be used as a surrogate for a chemical with a less rapid migration. Generally,
OSHA suspects that use of analogous chemical structures may be less accurate than other
methods and should be used only when better information is not available. However, OSHA
believes that use of analogous chemical structures would be infallible so long as objective data or
information for lower molecular weight compounds is used to predict the break-through times for
higher analogous molecular weight compounds containing only additional methyl or phenyl
groups. Analogous chemical structures should not be used to predict break-through of analogous
substances that have a lower molecular weight.

Experimental Testing

The ideal cartridge change-out schedule would be based on laboratory test data, which was
developed at the same conditions at which the cartridge is to be used. However, it is usually
difficult, time-consuming, and expensive to obtain this type of information for the range of

3
workplace variables. A method for conducting field-testing in the workplace is discussed in
Attachment 3.

NIOSH certifies organic vapor cartridges using the criteria in 42 CFR 84, Approval of
RespiratoryProtective Devices. Still, there is no widely accepted, standard protocol for
performing service life testing. However, both the Environmental Protection Agency (EPA) and
OSHA have published recommendations for performing service life testing. These methods can
be found at OSHA's website:

(a) http://www.osha-slc.gov/SLTC/etools/respiratory/oshafiles/h049.html
(b) http://www.osha.gov/SLTC/etools/respiratorv/testing/testing.html

Manufacturer's Data

Manufacturers are likely to possess the most accurate data for their own respiratory products.
However, the manufacturer may not have tested the respirator with the chemicals or
environmental conditions that you work with, and therefore may not be able to offer a reliable
recommendation. Since their recommendations are based on the characteristics of their
cartridges, the recommendation may not be valid for other manufacturer's cartridges due to-for
instance-different carbon micropore volumes. Besides respirator manufacturers, objective data
for a particular make and model of the respirator cartridges sometimes can be obtained from
industry organizations, trade associations, professional societies, chemical manufacturers, or
academic institutions.

The September 2001 NIOSH Certified Equipment List (CEL) for respirators includes 78
manufacturers. Not all of these manufacturers have respirators with cartridges, and the ones who
do vary in the level of support that they can provide. Attachment 5 contains a list of air-purifying
respirator manufacturers (not all inclusive).

Mathematical Models
Mathematical equations have been used to predict the service lives of organic vapor respirator
cartridges to varying degrees of accuracy. There are differences in the models, and some are
more difficult to solve. Moreover, certain variables of equations are considered proprietary by
some respirator cartridge manufacturers and are not released to the general public. Unfortunately,
no one physical characteristic (e.g., boiling point, vapor pressure, molecular weight,
polarizability, etc.) of the contaminant (gas or vapor) or the sorbent has been identified that
consistently correlates with adsorption capacity and service life. Attachment 6 lists some factors
known to be important.

Mathematical models may be generally classified into two categories: predictive and descriptive.
Predictive models estimate the breakthrough time based on chemical and physical properties of
the contaminant whereas descriptive models attempt to fit mathematical equations to existing
experimental data. Predictive models can be useful to initially screen whether a cartridge might
be appropriate for a new chemical substance. If the model predicts service life at less than 20

4
minutes for the new chemical substance, then an organic vapor cartridge may not be appropriate
for the substance.

Gerry 0. Wood, of Los Alamos National Laboratory, has developed a predictive model. Use of
the Wood model is demonstrated in Attachment 7. A predictive model uses less data to "predict"
cartridge performance than descriptive models, which is why predictive models have a higher
percentage of errors associated with them. The model currently only considers dry conditions
(relative humidity <50%). Relative humidity is such a complex issue that presently no published
predictive models take it into account. The Wood model does not predict breakthrough times for
mixtures of materials and cannot be used for inorganic gases. This estimation showed 95%
confidence intervals of up to ±50% compared to experimental values.

The preamble to the OSHA respirator standard states "predictive models areprobably not likely
to present an acceptable alternative for most employers, and their use would require that a
considerable margin of safety be incorporated into any change schedule developed from such
estimation techniques." Thus, one should not rely on the Wood model without some
experimental confirmation of the calculation and/or use of appropriate safety factors (i.e.,
subtract at least a 50% error rate from the calculated result).

The effect of relative humidity on service life of organic vapor cartridges will depend on the
relative humidity level, the chemical concentration, volatility of the chemical, and the chemical's
miscibility (ability to dissolve) in water. The early work by Gary Nelson of Lawrence Livermore
Laboratory in 1976 established a breakthrough time multiplier (correction factor) of about 0.48
for cartridges preconditioned and tested at 90% relative humidity relative to cartridges
preconditioned and tested at 50% relative humidity. Based upon relatively few studies, OSHA
recommends that a reduction by a factor of two in the cartridge service life originally estimated
based upon 50% relative humidity, may be made when the relative humidity reaches 65%. If the
relative humidity exceeds 85%, OSHA recommends experimental testing or another method to
more specifically determine the service life. Attachment 8 shows what 3M recommends as a
correction factor for relative humidity based on volatility.

Two applications of the Wood model are available at OSHA's website. The first is a table (see
attachments 9 and 10) of breakthrough times for chemicals at several concentrations. The
breakthrough estimates in the table were calculated using "generic" values for the cartridge and
workplace input parameters. Therefore, the table does not provide the most accurate
breakthrough estimates. OSHA's "Advisor Genius" (see Attachment 11) allows the user to enter
specific values for the input parameters to improve the accuracy of the service life estimate.
Default values may be used if the actual values are unknown. In addition, the "Advisor Genius"
allows calculation of breakthrough times for any organic compound that is a liquid at room
temperature and for which certain parameters are known.

Mixtures

Change schedules are very difficult to develop for mixtures using predictive mathematical
models. Cartridge breakthrough may occur earlier in the presence of mixtures than would have

5
been predicted from data for a single compound. Cartridge service life for mixtures is best
determined using experimental methods. There is no accepted method for estimating the service
life of cartridges used in an atmosphere containing a mixture of vapors. However, OSHA's
Compliance Directive CPL 2-0.120, Inspectionproceduresfor the RespiratoryProtection
Standard,suggests if the breakthrough times for the individual vapors in a mixture are within one
order of magnitude, the individual vapor concentrations should be added together. It can then be
assumed that the entire mixture behaves like the contaminant with shortest breakthrough time. If
breakthrough times for the individual components vary by two orders of magnitude or more, the
service life estimate should be based on the contaminant with the shortest breakthrough time. It
is not known how well these simple rules predict cartridge service life in a mixed vapor
atmosphere.

Research by Coreen A. Robbins suggests that service time for individual vapors in a mixture is
related to their mole fractions in the mixture. The mole fraction for each chemical in a mixture is
equal to the concentration of that material (in ppm) divided by the total concentration of the
mixture. The service life for each component in the mixture is calculated by multiplying its mole
fraction by its predicted "single substance" service time. Simply stated, this method estimates
when the first component of a mixture will break through. An example on how to calculate
service life for a mixture is in Attachment 12.

Descriptive models use experimental data to calculate parameters that fit the model to the data.
Once the model is fit to a set of experimental data, the model is used to calculate values for
points where experimental data are not available. The validity of the model is dependant on the
accuracy of the experimental data, and some descriptive models may not account for all
significant variables (e.g., humidity, temperature, etc.).

The Yoon-Nelson descriptive model assumes each contaminant breakthrough profile (the plot of
percentage breakthrough versus time) is a symmetric sigmoidal curve. The experimental data
closely follow sigmoidal breakthrough curves in the breakthrough percentage range 0-50%.
However, at higher breakthrough percentages, the deviation of experimental data from symmetric
breakthrough increases, particularly-at high humidity and low concentrations. The confidence
level is much higher for the Yoon-Nelson model (±10%) than the Wood model. However,
certain parameter values first have to be derived from empirical data for each combination of
cartridge type, humidity condition, temperature, and contaminant. For a fee, the Miller-Nelson
Research Inc. in Monterey, California (http://www.millernelson.com/, phone number: 831-647-
1551) will determine these parameters and the cartridge service life for a particular situation.

Software

Computer software is becoming a major tool to help determine the service life of respirator
cartridges used to protect workers against airborne gas and vapor hazards. It's important to know
the limitations and understand the results of the software program used. Most of the programs
are similar, providing the user with input boxes to select a specific value or enter data on a
chemical, its concentration in the workplace, the cartridge type, breakthrough concentration,
temperature, humidity, and work rate. The better programs also require the user to input data on

6
atmospheric pressure, select a safety factor, and integrate the specific relative humidity as a
parameter. Because these software programs cannot know each workplace situation, they can
provide only estimates--not exact predictions. User estimates of work rates and measurements of
contaminant concentrations, as well as temperature and humidity, can further affect accuracy.
Summaries of software features are in Attachments 13 and 14. Attachment 15 compares the
calculated breakthrough times for various cartridges.

The first software program available was 3M's Respirator Service Life Software (based on the
Wood Model), released soon after OSHA revised its respirator standard. OSHA's "Advisor
Genius" also is based on the Wood model. OSHA's program includes default values for
cartridge and carbon characteristics, or users can enter their own values based on information
obtained from the respirator manufacturer. Using the manufacturer's data results in a more
accurate breakthrough estimate. AO Safety's "Merlin" software program is a spreadsheet.
Merlin calculates breakthrough times for either inorganic gases or organic vapors based on the
Wood model. Merlin uses a single screen for both data entry and results and provides a list of
chemicals. North Safety's "esLife" software has an optional screen to allow the user to enter a
job and workplace description, thus providing a printed record of the breakthrough calculation.
Willson's service life program (available on CD only) is based on the mathematical model by
Nelson. Survivair's "Air Purifying Respirator Cartridge Service Life Program" also uses Nelson's
model for the organic vapors. Moldex, US Safety, and Scott do not have calculator programs but
do have tables of breakthrough times. The MSA claims it's "Cartridge Life Expectancy
Calculator" is accurate to within ±25% of the experimental test values.

Users should be aware of the idiosyncrasies of the program they use. For example, finding a
chemical can be a challenge in some of the programs. Methyl ethyl ketone and MEK are
common synonyms for 2-butanone. Searching for MEK in certain programs will bring up this
material. In the other programs, common names and synonyms are not listed in the search
mechanism, making a CAS registry number search a better option. However, not all programs
have the capability to search by CAS registry number. Each program may handle specific issues
differently, requiring caution on the part of the user. For example, OSHA's standards dictate the
frequency of cartridge change depending on the substance, such as benzene. For this reason, most
of the programs do not calculate a breakthrough time or alert the user to the presence of a
standard. Using a cartridge longer than allowed by an OSHA standard can result in a citation.
Only some programs will issue a warning and refuse to calculate a breakthrough time if the user
enters a concentration greater than the IDLH. The values for IDLH, PELs, and other standards
may or will likely change over time, which means not all the information in the software program
should be assumed to be accurate.

Most software programs warn about the potential for desorption or stipulate not to use a cartridge
for more than one work shift. When organic materials with a boiling point below 65 0 C are
imbedded in a carbon filter, some may have a tendency to migrate through the sorbent material
during periods of storage or when not in use. This can rapidly increase breakthrough and could
present an additional exposure to the user. Whenever migration is possible, canisters and
cartridges should be changed after every work shift. The American National Standards Institute
(ANSI) Z88.2-1992, Practicesfor RespiratoryProtection,recommends desorption studies unless

7
cartridges are changed daily. OSHA's CPL 2-0.120 states that where contaminant migration is
possible (chemicals with boiling points below 65°C), respirator cartridges should be changed
after every work shift where exposure occurs. If the employer has specific objective data
(desorption studies) showing the performance of the cartridge under the conditions and schedule
of use/nonuse found in the workplace, daily change would not be required.

Limitations

Less volatile chemicals can cause desorption and subsequent early breakthrough of poorly
adsorbed, more volatile chemicals. For example, a maintenance worker wears a respirator for
exposure to chemical A. The use period is shorter than the service life for chemical A so no
breakthrough occurs. The next day the worker goes to a different area with exposure to a
different organic chemical, chemical B. Chemical B is less volatile than chemical A. Since the
service life was not used up with chemical A, the organic vapor cartridges are reused. Before
chemical B breaks through, it displaces the more volatile chemical A. If the change schedule
does not consider this effect, chemical A may break through and the worker is exposed to
chemical A. Laboratory studies by Yoon and Nelson have shown that a more strongly adsorbed
chemical can displace a relatively weakly adsorbed chemical.

Using 65°C as the indicator for migration does not take into account those materials that may
migrate after slightly longer periods of nonuse. A case where very nonvolatile chemicals desorb
to cause an overexposure might occur when emergency responders store their cartridges for use
for another day. For instance, the National Fire Protection Association (NFPA) standard 77,
Standardon Protective Clothing and Equipmentfor Wildland Fire Fighting,considers wildfire
smoke not immediately dangerous to life and health (IDLH) even though the human health
hazards have not been quantified. Under the standard, firefighters are allowed to wear air-
purifying respirators with High Efficiency Particulate Air (HEPA) filters by themselves or also
with organic vapor/acid vapor cartridges to fight wildland fires.

Some Considerations for Specific AF Jobs

Some Air Force personnel use organic vapor cartridges as an emergency escape mechanism from
fuel cells. There are several elements involved in the use of this type of respiratory protection
that may fail to adequately support escape. First, this escape mechanism assumes adequate
oxygen is available inside the fuel cell. This may not be an adequate assumption. Depending on
the procedure in progress and the reason for the loss of breathing air, insufficient oxygen to allow
worker escape may exist. For example, if a power outage leads to failure of the breathing air
pump, the ventilation system used to air out the cell could also fail. As a result, oxygen levels
inside the cell could drop, leading to an oxygen deficiency. Second, even if adequate oxygen is
available, the probability of worker escape will depend on the concentration of vapors in the cell,
the adsorption capacity of the cartridges, and the position of the worker when the failure occurs.
If the cartridge has been in service for a prolonged period of time the adsorption capacity will be
greatly diminished. Elevated vapor concentrations inside the cell could overload the cartridge;
therefore, the mask would not have enough adsorptive capacity left for safe escape.

8
Paragraph 3.4.12.1 of AFI 32-1052, Pest Management Program,requires all pesticide applicators
to be enrolled in the respiratory protection program. The EPA states in the Federal Register, 40
CFR Part 170.240(f)(7), Worker Protection Standard,that the employer shall assure that when
gas- or vapor-removing respirators are used, the gas- or vapor-removing canisters or cartridges
shall be replaced:
(a) At the first indication of odor, taste, or irritation.
(b) According to manufacturer's recommendations or pesticide product labeling,
whichever is more frequent.
(c) At the end of each day's work period, in the absence of any other instructions or
indications of service life

Contrary to AFOSH Standard 48-137, a June 1999 AFMOA memorandum stated, "Bases are
authorized to determine respiratory protection for spraying isocyanate containing paints based on
process-evaluation, measured exposure levels, and assigned protection factors (APFs)."
Diisocyanates often form condensation aerosols when they are airborne. For this reason, it is
generally necessary to use a particulate filter in combination with an organic vapor cartridge. If
other organic vapors are present in the same atmosphere as a diisocyanate, those vapors
invariably break through first.

Venkatram Dharmarajan of Bayer Corporation studied the breakthrough of hexamethylene

diisocyanate (HDI) through MSA GMA type and North N7500-1 cartridges at various relative
humidities and solvent saturation. Their results suggest these cartridges provide protection
against a challenge concentration of 100 ppb HDI (in a solvent mixture of 60% n-butyl acetate,
30% propylene glycol mono methyl ether acetate, 5% toluene, and 5% methyl ethyl ketone) at
relative humidities as high as 80% and as low as 20% at room temperature. No evidence of
desorption or migration was seen in cartridges that were repeatedly exposed to HDI atmospheres
day-after-day for six days. However, other paint ingredients might lead to breakthrough or
desorption in other scenarios.

9
 References

3M Technical Data Bulletin #142, "Reuse of Organic Vapor Chemical Cartridges," May 1999.

Culp, K. W.: Determining Organic Vapor CartridgeBreakthrough Characteristicsof JP-8

DuringAircraft Fuel Tank Entry Operations,thesis at West Virginia University, Morgantown,
West Virginia, (2000).

Dharmarajan, V., Lingg, R. D., and Myer, H. E.: "Evaluation of Organic Vapor Respirator
Cartridge Efficiency for Hexamethylene Diisocyante Vapor in the Presence of Organic Solvents,"
Applied Occupationaland Environmental Hygiene, Vol 16(3): 397-404 (2001).

Jonas, L. A., Sansone, E. B. and Farris, T. S.: "Prediction of Carbon Performance for Binary
Mixtures," American IndustrialHygiene Association Journal,44: 10,716-10,719 (1983).

Myers, W. R., DHHS NIOSH Publication 87-108, NIOSH RespiratorDecision Logic, 1987.

Nelson, G.O.: and A.N. Correia: Respirator Cartridge Efficiency Studies: VIII, Summary and
Conclusions, American IndustrialHygiene Association Journal,37, 197, pp. 514-525 (1976).

Nelson, T.J. and Janseen L. L.: "Developing Cartridge Change Schedules: What are the
Options?" 3M Job Health Highlights, 17(1): 1-5 (1999).

OSHA's website for Respirator Change-out Schedules:

http://www.osha.gov/SLTC/respiratornprotection/changeout.html

Robbins, C. A. and Breysse, P. N.: "The Effect of Vapor Polarity and Boiling Point on
Breakthrough for Binary Mixtures on Respirator Carbon," American IndustrialHygiene
Association Journal,57(8): 717-726 (1996).

Tharr, D.: "Application of Cohen and Garrison's Respirator Cartridge Service Life Prediction
Model to 1,6-Hexamethylene Diisocyanate (HDI) Monomer," Applied Occupationaland
EnvironmentalHygiene, 15(3): 245-248 (2000).

Wood, G.O.: "Estimating Service Lives of Organic Vapor Cartridges," American Industrial
Hygiene Association Journal,55(1): 11-15, (1994).

Yoon, H. Y. and Nelson, J. H.: "Application of Gas Adsorption Kinetics-il. A Theoretical Model
for Respirator Cartridge Service Life and its Practical Applications," American Industrial
Hygiene Association Journal,45: 517-524 (1984).

Yoon, H. Y. and Nelson, J. H.: "Respirator Cartridge Service-Life: Exposure to Mixtures,"

American IndustrialHygiene Association Journal,57: 809-819 (1996).

10
 Attachment 1. Estimating Cartridge Service Life Flowchart

Particulate and/or oily aerosols

Contminat 0,No Change-out Schedule
Contamineict-Required. Change-out when
breathing becomes difficult.

Type of Gas or I i Use a cartridge with an End-of-

Vapor Such as an Acid or Base Service-Life-Indicator (ESLI).

Organic

Use OSHA's Math Model Table.

Note that use of this table usually
I only have means that the cartridges will be
time to Ychanged at a faster rate than
accomplish the Ynecessary
minimum _
requirements.

The ideal cartridge change out

schedule is based on experimental
laboratory testing, which is
conducted at the same conditions
to be aat which the cartridges will be
saccurate
as used.

No

Use the cartridge manufacturer's software program or table. If the manufacturer has no
software program or table, use OSHA's Advisor Genius with the conservative default
cartridge properties. If the manufacturer only provides a table to use, safety factors will
need to added.

11
 Attachment 2. Cartridge Service Life for OSHA Substance-Specific Standards

OSHA Standard Change Schedule

Acrylonitrile If air-purifying respirators (chemical-cartridge or chemical-canister types) are used:
29 CFR 1910.1045(h)(2)(ii) -- The air-purifying canister or cartridge must be replaced prior to the expiration of its
service life or at the completion of each shift, whichever occurs first.
-- A label must be attached to the cartridge or canister to indicate the date and time at
which it is first installed on the respirator
Benzene For air-purifying respirators, the employer must replace the air-purifying element at
29 CFR 1910.1028(g)(2)(ii) the expiration of its service life or at the beginning of each shift in which such
elements are used, whichever comes first.
If NIOSH approves an air-purifying element with an ESLI for benzene, such an
element may be used until the indicator shows no further useful life.
1,3-Butadiene If air-purifying respirators are used, the employer must replace the air-purifying filter
29 CFR 1910.1051 (h)(2)(ii) elements according to the replacement schedule set for the class of respirators listed
in Table 1 of the standard, and at the beginning of each work shift.
Instead of using the replacement schedule listed in Table 1 of the standard, the
employer may replace cartridges or canisters at 90% of their expiration service life,
provided the employer:
-- Demonstrates that employees will be adequately protected by this procedure.
-- Uses breakthrough data for this purpose that have been derived from tests
conducted under worst-case conditions of humidity, temperature, and air-flow rate
through the filter element, and the employer also describes the data supporting the
cartridge-or canister-change schedule, as well as the basis for using the data in the
employer's respirator program.
A label must be attached to each filter element to indicate the date and time it is first
installed on the respirator.
If NIOSH approves an ESLI for an air-purifying filter element, the element may be
used until the ESLI shows no further useful service life or until the element is replaced
at the beginning of the next work shift, whichever occurs first.
Regardless of the air-purifying element used, if an employee detects the odor of BD,
the employer must replace the air-purifying element immediately.
Formaldehyde If air-purifying chemical-cartridge respirators are used, the employer must:
29 CFR 1910.1048(g)(2)(ii) -- Replace the cartridge after three hours of use or at the end of the workshift,
whichever occurs first, unless the cartridge contains a NIOSH-approved ESLI to show
when breakthrough occurs.
-- Unless the canister contains a NIOSH-approved ESLI to show when breakthrough
occurs, replace canisters used in atmospheres up to 7.5 ppm (10xPEL) every 4 hours
and industrial-sized canisters used in atmospheres up to 75 ppm (100xPEL) every 2
hours, or at the end of the workshift, whichever occurs first.
Methylene chloride Employers who provide employees with gas masks with organic-vapor canisters for
29 CFR 1910.1052(g)(2)(ii) the purpose of emergency escape must replace the canisters after any emergency
use and before the gas masks are returned to service.
Vinyl chloride When air-purifying respirators are used:
29 CFR 1910.1017(g)(3)(ii) -- Air-purifying canisters or cartridges must be replaced prior to the expiration of their
service life or the end of the shift in which they are first used, whichever occurs first.
-- A continuous-monitoring and alarm system must be provided when concentrations
of vinyl chloride could reasonably exceed the allowable concentrations for the devices
in use. Such a system must be used to alert employees when vinyl chloride
concentrations exceed the allowable concentrations for the devices in use.

12
 Attachment 3. Field Testing of Cartridge Effectiveness for a Contaminant

In the workplace, collect an air sample behind the cartridge using a Portacount® mask
sampling adapter. Collect these samples in the same workplace where the respirator use
is required and while the process is ongoing. The sampling method (e.g., flame ionization
detector, photoionization detector, hydrocarbon detector tubes, gas chromatograph,
charcoal tube, etc) does not have to be specific for each component of the mixture but it
should be sensitive enough to detect concentrations at 25 % of the occupational exposure
limits of the mixture components. If no organic vapors are detected then the change out
schedule is verified. A list of mask sampling adapters available from respirator
manufacturers is provided in Attachment 3. Install the Portacount® mask sampling
adapter an area free of contaminated air, then return to the worksite to collect the sample
behind the cartridge while the respirator is being worn by the worker.

Portacount® mask sampling adapter

Adapler3s lnhaaflOn Va-•e

To PORTACOUNTr / Re.pratof,
inhalakon Valve Sample Inlet

Sampling Adapter ClIP

Detach the "Sample Tube" along with the "Suction Cup" and "Clip." Install the
Portacount® mask sampling adapter between the facepiece and the cartridge. Attach
tubing to the outside fitting of the Portacount® mask sampling adapter. Close off the end
of this tubing with a heavy wire paper clip to prevent contaminated air from entering.
Have worker redon the respirator. When back in the worksite, remove the clip and attach
the sampling device to the end of this tubing. In this arrangement, the air sample will be
collected in the chamber between the inhalation valve of the Portacount® mask sampling
adapter and the inhalation valve of the facepiece. If there are no organic vapors detected
in the samples then significant breakthrough (> 25% occupational exposure limit) has not
occurred and the change out schedule is confirmed. Change cartridges according to the
estimated (now verified) change out schedule.

It is not necessary for the Air Force to purchase any additional air sampling equipment to
collect air samples behind respirator cartridges for verifying cartridge change out
schedules. It is acceptable to collect air samples on sorbent tubes behind the cartridges at
the highest flow rate allowed by the sampling method. This permits relatively quick

13
collection of the lowest sample volume, for laboratory analysis results that can be
reported in concentrations down to the limit of detection. Most air samples can be
collected behind cartridges in five to ten minutes.

Pictorial Example

The following pictures show a quantitative fit-testing (QNFT) adapter such as the 3M
601 Quantitative Fit Testing Adapter is mounted between the cartridge and the facepiece.

The sample tubing is normally passed

through a respirator's inhalation valve for
sampling inside the facepiece during
quantitative fit testing.

The tubing that is normally passed through the respirator's inhalation valve to draw a
sample from inside the facepiece is removed.

The 3M 601 Adapter with the sample

tubing removed. The arrow points to the
exposed end of the hose connector,
which draws samples from the air space
between the cartridge and the facepiece.

This allows the space between the inhalation valves on the 3M 601 Adapter and the
respirator (i.e. between the cartridge and the respirator) to be sampled. A short piece of
tubing is attached to the outer hose connection on the adapter to allow connection of a
sampling device. The tubing is held closed with a pinch-style paper clip until the
sampling device is connected.

14
 The 3M 601 Adapter positioned for
sampling behind the cartridge. The
tubing is pinched closed until the air
sample is taken.

Any sampling method with sufficient sensitivity to detect the chemical of interest at a
concentration below the exposure limit can be used to take the sample.

Sampling behind the cartridge with a

colorimetric detector tube.

Since use of the QNFT adapter temporarily voids the respirator's NIOSH approval, it may
be put in place for only a short (-30 minute) equilibration period prior to sampling

The U.S. Navy Environmental Health Center (NAVENVIRHLTHCEN) performed an

experiment to determine if workers' breathing would interfere with the flow rate of
sampling pumps while collecting air samples behind the cartridges. An analysis of
variance (ANOVA) test of the experimental results showed that there is no significant
difference (PO. 05) between the average flow rate of pumps collecting air samples in
ambient atmosphere and pumps collecting air samples inside Portacount® mask sampling
adapters connected to workers' respirators while they breath normally. However,
ANOVA indicated that there is a significant difference (PO. 05) between those two means
and the mean flow rate of pumps collecting air samples inside PortacountV mask
sampling adapters connected to workers' respirators while they are breathing hard. When
an air sample is collected behind a cartridge inside a Portacount® mask sampling adapter,
the worker must breath normally so as not to interfere with collection of the sample.
Instruct the worker to take a break for five to ten minutes while wearing the respirator in
the worksite during air sample collection. The workers' normal breathing will not
adversely influence detection of breakthrough. By the time of air sample collection, all of
the varying air contaminant concentrations, varying temperature and humidity, and
varying breathing rates throughout the day have already had their influence on respirator

15
cartridge breakthrough. In other words, workers breathing normally right before cartridge
change out time would not significantly influence breakthrough - breakthrough would
have either already occurred or not occurred.

Gary 0. Nelson and Charles A. Harder of Lawerence Livermore Laboratory evaluated the
service life of organic vapor cartridges using a mechanical breathing simulator for
pulsating flow rates. In regards to experimental testing, no significant difference were
observed between steady state and pulsating-flow patterns, even at equivalent high work
rates and humidity conditions. It is speculated that the equilibrium between the solvent
vapor and the charcoal is so rapid that little or no difference exists between the both types
of flow.

References:

Industrial Hygiene Directorate of the Navy Environmental Health Center

http://www-nehc.med.navy.mil/ih/Respirator/ChangeSchedule.htm

Nelson, T. J., and Janssen, L. L.: "Developing Cartridge Change Schedules: What are the
Options?" 3M Job Health Highlights, Volume 17(1): 1-5 (1999).

Nelson, G. 0. and Harder, C. A.: "Respirator Cartridge Efficiency Studies IV. Effects of
Steady-State and Pulsating Flow," American IndustrialHygiene Association Journal,
Volume 33, 797-805 (1972).

16
Attachment 4. Mask Sampling Adapters Available from U.S. Respirator

Manufacturers

This is a list of adapters available from respirator manufacturers and their distributors. TSI offers many of
the same adapters, repackaged with HEPA filters and additional supplies, for direct sale.______
Respirator Model AdpeKi
Manufacturer__________________ Ad pe Telephone___________
Kit______________________________________
(H=Half, F=Full) - FPart No.Tepoe

[Comfo Series (H) [812022 CQuikChekl m Il)

Duo-Twin (F) [812022 (QuikChekTM II)

Ultra Twin (F) j812022 (QuikChek T

1 II)

Advantage 100/200/200LS (H) [812022 + 809999

Advantage 1000(F) [1062F8062

MSA MILLENIUM (F) 1062(0072-2
Ultra Elite CF) (screw-in version) 805078 (QuikChek TM III) +

[ADVANTAGE 3000 Series (F) j468

M
Ultra Elite (F) (1/4 turn version) 80508(ukhk
0 I n
I ý817446 (QuikChek T" IV)
Ultravue (F) (not for SCBA) f802710 (QuikChekT M I)

___________ Phalanx (F) f 802710 (QuikChek T

m'I)

5500 (H) 7700-21

[7700 Series (H) [7700-21

5400 and 7600 Series (F) 770-21(804-

Not 7800 Series j[7700-21 4110

85101, 85111, 85201, 85211 7700-21 with 7700-24

85400A, 85500A, 800 Series Pressure-Demand ~702 ih70-3ft

(F) [70-1wt 702 fiting

6000 Series (H/F) 601

7000 Series (H)(Bayonet) [601

7000Seres
H)(Cnvetioal)7930 (or use 601 with 9286
7000Seris ()(Coveniona) [adapters)
3M r7800 Series (F)(Bayonet) [601 (024630

f[7800 Series (F)(Conventional) 73 o s

[adapters)
0 ih99

7900 Series (F) [601

____________ F40 Gas Mask (F) 601 with 701

Screw Type (3-inch diameter): 1200(H), 1600(F), R9

~*Dalloz
Safety 170F,50()(800)345-
(Willson) 4112
Bayonet Type: 6100(H), 6200(H), 6400(F),
6500(F), 6800(H), 8100(F), 8600(F) R9

17
 "F" series facepieces with 1-inch diameter screw- 1232
*Glendale on filters 123(
Protective - (800)345-
rTechnologies "F" series facepieces with 3-inch screw-on filters [RP98 4112
(GPT) I!

Replacement Tubing (25) [1233

Scott-O-Vista (F) [803930-01

AV-2000 (F) j 803930-01

No adapter available. Order
Scott 66 Series (H) probed masks from Scott (800)247
(803550-??) 7257

Scottoramic (F) No adapter available. Order

Sprobe kit from Scott (803119-01)

XCEL (H) 7422-FT1

1490 Series (H) [QNFT Adaptor

9 S(800)375-
*Pro-Tech 1590 Series (H)1694 QNFT Adaptor 6020

Series (F) [QNFT Adaptor

AO Safety
(AEARO Company)
jAll models with screw-on filters
All models with bayonet filters
1 51171-00000 Adapter Kit*
[51172-00000
(800)225-
9038

Air Purifying Masks with Screw-on Filters, Fi

including 2000 420025 with 105005 Filter
Blue 1, Low Maintenance, 4000, 20/20, OPTi-Fit

Air Purifying Masks with Bayonet Filters, including 760075

Survivair OPTi-Fit, 7000 r r w277 7222
Positive Pressure/SCBA Masks with Panther-style 962920 and 962900 and Two
Mask Mounted Regulator, including Classic, 20/20 105005 Filters

Positive Pressure/SCBA (Mk-II) with Hose, N

including Classic, 20/20 See Appi. Note ITI-029

[#8006 (800)267-11
Moldex 8000 Series (H)

Spiroratic & Spirolite SCBA (F) [336-890-378 (800)468-

78
Interspiro
I7788
ISpiromatic "S" j95991

Sundstrom SR90(H) 702.120.99

Fit Test Kits:

171066 Small
Viking (SCBA) with Airswitch 171065 Medium
Vanguard (SCBA) with Airswitch 171067 Large
i ISI HEPA Filter:
33003(888)474-
I1ST ! 033003 73
7233

Ranger (SCBA) - 08925600

Not for pre-1986 version with 03407100 filter

Magnum (SCBA), Magnum Plus (SCBA) 08925600

18
 Panorama (F) cartridge version

Futura (F) cartridge version

Panorama (F) positive pressure (800)922-

Draeger
S.... .. _5518
Futura (F) positive pressure

Combitox Nova (H)

Cirrus (H)

Picco 20 (H) [4055655

Kit for all models [79200

*U.S. Safety A(800)252-
Adapter only 79210 5002

Refill Kit (for 100 fit tests) 79215

[C-Flex L-1561-75
Respiratory (800)378-
Systems, Inc. Lifeair STD L-4000-75 1000
Lifeair XL

* TSI 800553 Refill Kit can be used with these adapters

t TSI 800785 Refill Kit can be used with MSA Quik Chek I, II & III

19
 Attachment 5. Respirator Manufacturers
3M Company 1-800-243-4360 651-733-7364
http://www.3m.com/occsafety/html/cartridgechange.html

Aearo Corporation 1-800-444-4774 508-764-5787

http://www.aearo.com/html/products/respirat/respfor.htm

Draeger Safety 412-787-8383 412-788-5685

http://www.draeger.com/us/ST/productsnservices/protection/filters/filters.jsp

Mine Safety Appliance Company 1-800-MSA-2222 724-776-7775

http://www.msanet.com/msanorthamerica/msaunitedstates/cartlife/index.html

Moldex-Metrics, Inc 1-800-421-0668 310-837-6500

http://www.moldex.com/images/PDFs/CARTRIDGE.pdf

North Safety Products 1-800-430-4110 401-275-2445

http://www.northsafety.com/featurel .htm lhttp://www.northsafety.com/train.htm

Scott Health & Safety 1-800-633-3915 704-296-4562

http://www.scotthealthsafety.com/hsliterature/product.asp?sku=0899

Survivair, Inc 1-888-APR-SCBA 714-850-0299

http://www.survivair.com/cartlife.html

U.S. Safety 1-800-821-5218 913-599-5555

htt :I/www.ussafety.com/Cartridge Service Life.htm

Prior Name Current Name

AG Spiro Interspiro USA, Inc.
American Optical Aearo Corporation
Cabot Safety Corporation Aearo Corporation
Cesco U.S. Safety
Fastech Corp. Axis Products, Inc.
Glendale Protective Technologies, Inc. Willson ® Dalloz Safety
Products
H.S. Cover Pro-Tech Respirators, Inc.
National Draeger, Inc. Dr~ger Safety, Inc.
New England Thermoplastics Better Breathing, Inc.
Norton North Safety Products
Parmellee Willson ® Dalloz Safety
Products
Pirelli Dispositivi Protezione
Individuale D.P.I. SRL
Protector Technologies
Protector Technologies Europe Limited
Pulmoson Willson ® Dalloz Safety
Products
Racal Health and Safety, Inc. / Racal Panorama 3M Company
Rexnord Biomarine, Inc.
Robertshaw International Safety Devices,
Inc.
Safety & Supply Vinatronics, Inc.
Technol Kimberly-Clark Corporation
Trusafe, Inc. Vinatronics, Inc.

20
Attachment 6. Factors to consider when developing a cartridge change-out schedule.

The following is a partial list of factors which may affect the usable cartridge service life
and/or the degree of respiratory protection attainable under actual workplace conditions
- Type of contaminant(s)
Polarizability, dipole moment, quadrupole moment, etc. all have an effect.
In general, activated carbon has a greater affinity for less volatile materials.
The weight adsorbed is a decreasing function of the vapor pressure.
- Contaminant concentration
- Relative humidity
- Breathing rate
- Temperature
- Changes in contaminant concentration, humidity, breathing rate and temperature
- Mixtures of contaminants: (1) multiple contaminants present simultaneously versus
(2) alternate usage of the same cartridges against different contaminants on different
occasions.
- Accuracy in the determination of the conditions
- Cartridge storage conditions
Exposure to trace levels of contaminants and humidity and elevated temperatures.
- Storage conditions between multiple uses of the same respirator cartridges.
Contaminants adsorbed on a cartridge can migrate through the carbon bed without
airflow.
- Physical and chemical properties of the sorbent in the cartridge
Surface area, porosity, activity of sorbent, capacity of the sorbent all have an effect.
- Age of the cartridge
- Condition of the cartridge and respirator
- Respirator and cartridge selection
- Respirator fit
- Respirator assembly, operation, and maintenance
- User training, experience and medical fitness
- Warning properties of the contaminant
- Change schedules for contaminants with poor warning properties may require a greater safety
factor than a contaminant with good warning properties.
- Other conditions specific to the particular user and/or workplace

Properties which sorbents ideally posess are

- Ability to sorb contaminants at a high rate
- High capacity (quantity) for contaminant adsorption
- High retention for sorbate so as to minimize desorption
- Ability of sorbent granules to retain their shape and size so that they do not crush
- Stability and retention of these properties under normal storage conditions and use conditions.

21
 >) o

t4; j 2C)

cnn.

0 a)

vs) 4)d > C

ci, 0

P4: Cd -

w 0-~ c

0 o

o) a) 0

E 00

-- a)r %--O~a.

O0En,
U, 0 0 0Idc _' "
,.D
03 0 a ) 0

(0C co too
~~ 0. 50 rCZ

2 d Cd 2 0a
-4- cl 0
o~0 a Ed

00

--
ed~a a 0c rnc
II 'o "0 ed
-~a), OC 'Z tc -

P0J0 0* C cu
* Cd1

-l o u .- >

t4- 0 E

0a) -P C
0 0 4- -

+ 22
 .0.0 0

bo
C)d

C.))
C.)d

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CIS 4

C))

0 00
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C~C>

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0, +n 0n 03
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0 4- O?
00, CA

0O: 0

-u a) ýc

4-. 0- r-
~0 0o b 4.1 + H
CA C)'
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-k4 EC. .- 0-

0 C4-4 0
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(8 u C+cj,
'~Cd ~r
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0 6
- 4)~ ". 0. 0C>
0

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0) cd C.
C)0 .0 c ~ 0,
0, _
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p~C 04-4
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0. E 0, C
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23
 o

oo-l-

00-4-

,oCo

-~ 0

ý4-
cq --

oo-

00 0

- CrJ

C))
6 00
C.) 62 00S
00 in En

00 kn .04-C

C) kn(AC

C) C)

0~ Z
0C: 1
00 I- 0r3)

0 0 C) d El
C-404 :
C.):1 CD)

C:) 604) C
0
- a) C)~ - I
Im z 1C
>, C c0

0 0
0~ 4- -'-

- BýC~ C 0
-~Z -u I"-~

C24
 4- 0

CA) L•
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7:1 00
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up 00

00 00

00 0~0+

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"0 0 a 0 0
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-26
Attachment 8. Correction Factor versus Solvent Concentration at 85% Relative Humidity
and for 1% Breakthrough

-e- n-hexane
-- toluene
-- styrene
-- benzene
b- perchloroethylent
30

25 .

20

15 , ,,_ __
_, _ _ _ _

0 bz
110 -:---A ---- 2 i .......

0...-. ii--I -":i -- ,ii!i -

0 200 400 600 800 1000

concentration in ppm

These measurements were taken by 3M with 3M (model 6001) organic vapor cartridges. For
chemicals with low volatility such as styrene, the effect of high relative humidity is small. At
85% relative humidity, a correction factor of about 1.5 seems appropriate through the styrene
concentration range tested. For the more volatile chemicals tested, the most significant relative
humidity effect is at low concentrations. Using n-hexane as an example, at high concentrations
(- 400 ppm) the necessary correction factor for 85 % RH is about 2, whereas at low
concentrations (- 10 ppm) the service life estimate should be reduced by a factor of about 16.

ISolvent Vapor Pressure mmHg Boiling point Idegrees C

Fn-hexane i124 69
1Benzene '75 80
IToluene 21 110.6
SPerchloroethylene i14 1121
tyrene [45-146

27
 Attachment 9. The Wood Math Model Table

The table below provides breakthrough times for chemicals at various concentrations. OSHA
derived these breakthrough times from the Gerry 0. Wood math model (Wood, G.O.,
"Estimating Service Lives of Organic Vapor Cartridges", American IndustrialHygiene
AssociationJournal, 55:11-15, 1994).
OSHA used the following standard conditions:
- Relative humidity: less than or equal to 50%
- Sorbent mass per cartridge: 26 g
- Flow rate: 53.3 liters per minute
- Breakthrough: 10%
- Number of Respirator Cartridges: 2
- Temperature: 22 degrees Celsius (72 degrees Fahrenheit)
- Sorbent: Activated Charcoal
If the conditions in your case are significantly different than these, in particular relative
humidity greater than 65%, you will need to make appropriate corrections to the times in the
table. This table is at the following website:
http://www.osha.gov/SLTC/etools/respiratorv/wood table/wood table.html

Name CAS # Contaminant Concentration (ppm)

50 100 200 500 1000
Aromatics
Work- Llmled to armaximum lrao o Tur
Benzene 71-43-2 Shift negative pressure APR
See the Benzene Standard 29 CFR 1910.1028(g)
Toluene 108-88-3 1018 562 307 135 72
Ethylbenzene 100-41-4 1133 604 319 135 70
m-Xylene 108-38-3 1143 608 321 136 70
Cumene 98-82-8 1122 586 304 126 64
Mesitylene 108-67-8. 1159 603 311 128 65
p-Cymene 99-87-6 1104 566 289 117 59

Alcohols
Methanol 67-56-1 This calculation isnot applicable to this compund
Ethanol 64-17-5 123 105 85 60 43
Isopropanol 67-63-0 425 286 186 101 61
Allyl alcohol 107-18-6 789 495 303 152 87
Propanol 71-23-8 551 364 233 123 73
sec-Butanol 78-92-2 773 464 272 130 72
Butanol 71-36-3 1073 615 345 156 84
2-Pentanol 6032-29-7 1091 601 327 143 75
3-Methyl-l-butanol 123-41-3 1242 672 358 152 78
4-Methyl-2-pentanol 108-11-2 1076 578 307 130 67
Pentanol 71-41-0 1281 690 366 155 79

28
2-Ethyl-l-butanol 97-95-0 1246 657 342 142 72

Monochlorides
Methyl chloride 74-87-3 Not applicable, boiling point below ambient temperatures

Vinyl chloride 75-01-4 Not applicable, boiling point below ambient temperatures
See the Vinyl Chloride Standard 29 CFR 1910.1017(g)
Ethyl chloride 75-00-3 Not applicable, boiling point below ambient temperatures
2-Chloropropane 75-29-6 224 150 99 54 34
Allyl chloride 107-05-1 264 177 116 64 40
1-Chloropropane 540-54-5 492 301 181 90 52
2-Chloro-2-methylpropane 507-20-0 655 374 212 98 54
1-Chlorobutane 109-69-3 733 422 239 111 61
2-Chloro-2-methylbutane 594-36-5 705 398 222 101 55
1-Chloropentane 543-59-9 852 474 260 116 62
Chlorobenzene 108-90-7 1327 709 376 160 83
1-Chlorohexane 544-10-5 993 530 281 119 62
o-Chlorotoluene 95-49-8 1297 682 356 148 76
1-Chloroheptane 629-06-1 930 492 258 109 56
3-(Chloromethyl) heptane 123-04-6 771 410 216 92 48

Dichlorides
Dichloromethane 75-09-2 See the Methylene Chloride Standard 29 CFR 1910.1052(g)

trans- 1,2-Dichloroethylene 156-60-5 296 198 129 71 44

1,1-Dichloroethane 75-35-4 234 157 103 57 35
cis- 1,2-Dichloroethylene 156-59-2 356 236 152 82 50
1,2-Dichloroethane 107-06-2 482 310 194 101 60
1,2-Dichloropropane 78-87-5 776 452 259 121 67
1,4-Dichlorobutane 110-56-5 846 475 263 118 64

Trichlorides
Chloroform 67-66-3 409 263 166 87 52
Methyl chloroform 71-55-6 618 366 214 102 57
Trichloroethylene 79-01-6 749 441 256 122 68
1,1,2-Trichloroethane 79-00-5 976 558 314 143 77

Tetrachlorides
Carbon tetrachloride 56-23-5 677 398 231 109 61
Perchloroethylene 127-18-4 1106 609 331 145 77

Acetates
Methyl acetate 79-20-9 182 131 92 55 36
Vinyl acetate 108-05-4 389 251 158 82 49
Ethyl acetate 141-78-6 483 299 182 91 53

29
Isopropyl acetate 108-21-4 668 386 219 102 56
Propyl acetate 109-60-4 768 438 246 112 61
Butyl acetate 123-86-4 935 508 273 118 62
Isopentyl acetate 123-92-2 1007 530 277 116 59
Pentyl acetate 628-63-7 1023 537 280 117 59

Ketones
Acetone 67-64-1 118 92 69 44 30
2-Butanone 78-93-3 423 271 170 88 52
2-Pentanone 107-87-9 729 424 243 113 62
3-Pentanone 96-22-0 744 433 248 115 63
4-Methyl-2-pentanone 108-10-1 884 488 266 117 62
Mesityl oxide 141-79-7 1063 581 314 136 71
Cyclopentanone 120-92-3 1020 589 333 153 83
2,4-Pentanedione 123-54-6 1103 612 335 147 78
3-Heptanone 106-35-4 1061 561 294 123 63
2-Heptanone 110-43-0 791 432 234 102 54
Cyclohexanone 108-94-1 1257 683 366 157 81
Diisobutyl ketone 108-83-8 963 496 254 103 52

Alkanes
Pentane 109-66-0 332 205 124 63 37
45
533 307 175 82
2,3-Dimethylbutane 79-29-8
Hexane 110-54-3 585 334 189 87 48
Methylcyclopentane 96-37-7 613 357 205 96 53
2,2,4-Trimethylpentane 540-84-1 747 401 214 92 48
Heptane 142-82-5 769 420 227 99 52
Methylcyclohexane 108-87-2 842 463 252 111 59
2,2,5-Trimethylhexane 3522-94-9 817 429 224 93 48
Cyclooctane 292-64-8 747 410 224 99 53
Nonane 111-84-2 907 470 242 100 51
Decane 124-18-5 902 461 234 95 48

Amines
Methylamine 74-89-5 Not applicable, boiling point below ambient temperatures
Dimethylamine 124-40-3 Not applicable, boiling point below ambient temperatures
Ethylamine 75-04-7 Not applicable, boiling point below ambient temperatures
Isopropylamine 75-31-0 167 117 80 46 30
Propylamine 107-10-8 226 155 104 59 37
Diethylamine 109-89-7 498 299 177 86 49
Butylamine 109-73-9 580 349 207 100 57
Triethylamine 121-44-8 747 412 225 100 53
Dipropylamine 142-84-7 871 474 255 111 58

30
Diisopropylamine 108-18-9 716 395 216 96 51
Cyclohexylamine 108-91-8 1065 575 308 132 69
Dibutylamine 111-92-2 980 507 261 107 54

Miscellaneous I I I I
Methyl iodide 74-88-4 This calculation is not applicable to this compund

Acrylonitrile 107-13-1 Work 1ILimited to a maximum concentration of 100

Shift_- 465 ppm
See the Acrylonitrile Standard 29 CFR 1910.1045(h)
Dibromomethane 74-95-3 947 565 331 158 89
Pyridine 110-86-1 1031 599 342 158 87
Epichlorohydrin 106-89-8 866 525 310 150 84
1,2-Dibromoethane 106-93-4 1252 699 384 170 90
1-Nitropropane 108-03-2 933 548 315 147 80
2-Ethoxyethanol 110-80-5 1105 624 345 154 81
Acetic anhydride 108-24-7 1095 623 348 156 83
2-Methoxyethyl acetate 32718-56-2 1092 594 319 137 71
Bromobenzene 108-86-1 1448 761 397 165 84
2-Ethoxyethyl acetate 111-15-9 1143 600 312 129 65

31
 Attachment 10. OSHA's Example on how to use a Math Model Table

The Wood model table can be found in Attachment 7. The math models are usually only directly
applicable for single contaminant exposures. If you have a multiple contaminant situation, you
may need to use other methods to derive a schedule or increase the safety factors. Since the
Wood model is not a descriptive model, it is suggested that you reduce the service life estimate
by some safety factor to give a change schedule that you should document in your written
respiratory program.

Steps Example
1, Determine the concentration level Grant owns a mid-size furniture company that paints with
•of airborne contaminants in the work lacquers. They use a volatile solvent, toluene to quickly
dry the lacquer. His several measurem entsSarea
of the
toluene vapor reveal a worst case exposure of 200 ppm
over an eight-hour day.

2. Obtain access to a predictive table IGrant surfs to the web page on this Advisor site called
that is based on research IWood Model Table, which lists cartridge service lives for
120 chemicals at varying concentrations.
3. Use the table to come up with a Grant looks across the top of the table and finds the
cartridge service life estimate column for 200 ppm - the concentration equal to or
above the level of toluene at his work place. Then he
scrolls down the table and finds toluene in the aromatic
group. He discovers that the service life estimate is 307
minutes. He writes down the number.
4. Account for differences in the real Grant looks at the standard conditions given at the top of
work environment and those the table. He sees that the assumed relative humidity is
assumptions used by the math model 50% - much lower than the 75% humidity found in his
work area. Grant is aware that such a high humidity will
* humidity and temperature seriously affect organic vapor cartridge performance, so
* breathing rate he applies a safety factor of two by cutting the estimate in
half, giving him 154 minutes. The other standard
conditions assumed by the table match his work
environment.
5. Create a written change schedule Grant applies a further safety factor to the estimate and
for the cartridges creates a change schedule requiring his employees to
turn in their used cartridges for new ones every 2 hours.
He also prints a copy of the Wood Model Table and
circles the 307 minute value and notes the factor applied
for humidity and the safety factor reduction to 2 hours,
and includes them in his written respiratory program.

32
 Attachment 11. OSHA's Example on how to use a Math Model Equation

Mathematical equations have been used to predict the service lives of organic vapor respirator
cartridges when used for protection against single contaminants. The Wood Math Model is just
one equation you can use. Also, because it is a predictive type of model (as opposed to a
descriptive type), you should not rely on it without some experimental confirmation of the
calculation or use of appropriate safety factors.

OSHA's Advisor Genius web program will estimate the contaminant breakthrough time for an
activated carbon respirator cartridge using physical and environmental parameters specific to the
contaminant and the workplace. It only applies to contaminants that are liquids at the workplace
temperature.

htti://www.osha.gov/SLTC/respiratory advisor/advisor genius wood/advisor genius.html

Steps ]Example
1. Determine the following: The lacquer-drying technique has been modified at
Grant's shop, which has lowered the amount of
* Number of cartridges used by the airborne toluene to 125 ppm. While this is below the
respirator OSHA PEL, Grant still wants his painters to wear
* Weight of sorbent in each cartridge respirators. When Grant looks to the Wood table
in grams for this concentration to figure a service life
* Carbon micropore volume in cubic estimate, he finds there is no column for 125. It
centimeters per gram gives data for 100 ppm and then jumps right up to
• Density of the packed bed in units 200 ppm. Grant understands that he must go with
of grams per cubic centimeter the 200 ppm estimate of 154 minutes to be safe,
* The maximum temperature yet he thinks the cartridges should last longer than
expected in the workplace that. He determines to use the Wood calculation
* The maximum humidity expected in for his exact concentration of 125 ppm. So, Grant
the workplace does a little research to come up with the required
* The maximum concentration of data. He calls the manufacturer to get data on its
contaminants in the workplace in respirator cartridges.
units of parts per million
The work-rate (volumetric flow rate)
in units of liters per minute (LPM).

2. Put the information from Step I into a Grant hears that the OSHA Advisor will perform the
mathematical equation and calculate for jcalculation for him. All he has to do is provide his
the unknown service life information to the Advisor Genius, which asks for
the data one step at a time. Grant is delighted with
how easy it is, and at the end, the Genius gives him
the service life estimate of 224 - 70 minutes
longer than if he had used the table.
3. Apply a safety reduction to the service Grant applies a safety reduction to the service life
life estimate, create a written change estimate and sets his change schedule at 3 hours.
schedule for the cartridges and include in The Advisor Genius also offers to print out a report
written respiratory protection program. for Grant that can serve as the basis for written
Ichange schedule as part of the respirator program.
Grant prints out the form, notes the adjustment
factors and is done!

33
 Attachment 12. How to Calculate Service Life for Mixtures

Employees in a coating line have 8-hour time-weighted average exposures to an atmosphere

containing the following mixture of solvents: 100 ppm for toluene, 75 ppm for MIBK, and 100
ppm for ethyl acetate. The job is classified as light work and relative humidity in the plant is
50%. 3M 6001 organic vapor cartridges are used. What is an appropriate cartridge change
schedule?
Answer:
3M Service Life software predicts the following "single substance" service times: 3,770 minutes
for toluene, 3,290 minutes for MIBK, and 2,480 minutes for ethyl acetate. These values
represent the times to reach 10% of the inlet concentration if the cartridges were exposed to each
contaminant individually.
OSHA method (see OSHA's Compliance Directive CPL 2-0.120):
Since breakthrough times are within one order of magnitude, the concentrations of the individual
contaminants are added and the total concentration is used to predict the breakthrough time:

100 ppm + 100 ppm + 75 ppm = 275 ppm

Since ethyl acetate has the shortest breakthrough time, it is assumed that the entire mixture
behaves like ethyl acetate. 3M Service Life Software predicts a service time of 989 minutes (16.5
hours) for 275 ppm ethyl acetate. Changing cartridges after each normal shift appears to be
appropriate.

Mole fraction method:

The mole fractions for the components of the mixture are calculated as follows:
Total ppm of mixture = 275 ppm.

- Toluene mole fraction = 100 ppm / 275 ppm = 0.36

- MIBK mole fraction = 100 ppm / 275 ppm = 0.36
- Ethyl acetate mole fraction = 75 ppm / 275 ppm = 0.27

Breakthrough times for the components as they exist in the mixture are then calculated:
fraction ~Single substance
Chemical IMole
S................ b rracton
r ug tim
. .... ... .. ... breakthrough te e .. ...Break- through
.. time in mixture
Toluene '0.36 13,770 min .1,360 min
MIBK 10.36 13,290 min 11,180 min
Ethyl 0.27 2,480 min 670 min
lace t at e

This method predicts earlier breakthrough than OSHA's method (670 minutes vs. 989 minutes).
Changing cartridges after each 8-hour shift still appears to be appropriate, but the margin of
safety is smaller. Since there is presently little data to support either of the methods used for
mixtures, sampling behind the cartridge near the end of the predicted use period is advisable to
confirm that the change schedule is correct.

34
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Attachment 16. Estimated Service Life for Cartridges Exposed to JP-8

250.0-
* 50%RHno
• 200.0 dpior exposure

* 80% RH, no.

150.0 prior exposure ......

. 100.0-

prior exposure
j50.0
-

0.0 , i , ,
100 300 500 700 900 1100 1300
Challenge concentration (parts per million)

(a) Vapor concentration

less than 300 ppm Breakthrough time
Below 50% 50-80% Above 80% relative
Desired change-out relative relative humidity or temp
concentration humidity humridit above 85 OF
17ppm (12 of proposed TL 2 hrs I hr 45 min.
25 Mm (112 of USAF OEL) 3 hrs 2 hrs 1 1/a hrs.

(b) Vapor concentration

300 to 600 ppm Breakthrough time
Below 50% 50-80% Above 80% relative
Desired change-out relative relative humidity or temp
concentration humidity humidit above 85 OF
7 ppm (12 of proposed TLV: I hr 35 min- 20 min.
25 ppm (I12of USAF OEL) 1/4 hrs I hr 45 min.

(c) Vapor concentration

600 to 1200 ppm Breakthrouqh time
Below 50% 50-80% Above 80% relative
Desired change-out relative relative humidity or temp
concent2ation humnidity 05
humdi3y 20
above F
7opm (et2 of proposed TLVii 35 tmin. 30 rmin- 20 5in-
25 Porn (1/2 of USAF 0EL) 40 rmmn. 1 30 min. 20 min-

Estimates are based upon the service life tested under laboratory conditions with 32 1pm through
each cartridge (equivalent to 64 1pm airflow through each set of cartridges). All cartridges were
preconditioned at 80% relative humidity and 25°C for six hours. (Note that these tests were
conducted when the OEL for JP-8 was 52 ppm).

Reference: Culp, K. W.: Determining Organic Vapor CartridgeBreakthrough Characteristics

ofJP-8 DuringAircraft Fuel Tank Entry Operations,thesis at West Virginia University,
Morgantown, West Virginia, (2000).

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 Attachment 17. Cartridge Properties

Carbon Weight of Sorbent Diameter

Micropore Sorbent in Bulk of Sorbent
Volume Cartridge Density Bed
(cm 3/gm) (gm) (gmlcm3 ) (cm)
MSA Comfo GMA 0.75 37 0.4 7.4
MSA Comfo GMC 0.55 48 0.51 7.4
MSA Comfo GME 0.35 72 0.62 7.4
MSA Advantage GMA 0.75 41 0.4 8.0
MSA Advantage GMC 0.55 52 0.51 8.0
MSA Advantage GME 0.35 75 0.62 8.0
North N7500-1 0.604 83.4 0.444 7.52
North N7500-3 0.49 93.8 0.5 7.52
North 75SC 0.346 140.6 0.59 7.52
Moldex 8100 ? 36.7 ? 7.85
Moldex 8600 ? 28 ? 7.85
Scott Organic Vapor Cartridges* 0.78 110 0.87 7.95
OSHA Default Values" 0.4 26 0.4 7

* Thevalues for the Scott Cartridges apply to all the models listed below:
- TC-23C-219 organic vapor only, full facepiece,air-purifying respirator
- TC-84A-271 1 organic vapor / P100, full facepiece, air-purifying respirator
- TC-84A-2858 organic vapor / N95, full facepiece, air-purifying respirator
- TC-23C-780 organic vapor only, half facepiece, air-purifying respirator
- TC-84A-2712 organic vapor/ P100, half facepiece, air-purifying respirator
- TC-84A-2855 organic vapor I N95, half facepiece, air-purifying respirator

** TheOSHA Default value of 7 cm for the diameter was calculated based on its
default value of 13 cm/sec for the linear flow rate at a breathing rate of 60 Ipm.

References:
http://www.moldex.com/images/PDFs/CARTRIDGE.pdf
http://www-nehc.med.navy.mil/ih/Respirator/ChangeSchedule.htm
http://warranty.msanet.com/safetyproducts/resptestlindex.html
http://www.osha.gov/SLTC/respiratoryadvisor/advisor genius-wood/calcframe.html

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