UNIVERSITY OF CINCINNATI

Date:______

I, ______, hereby submit this work as part of the requirements for the degree of: in:

It is entitled:

This work and its defense approved by:

Chair: ______

Comparison Study Between OSHA Rule of Thumb and Software Model Respirator Cartridge Service Life

Thesis submitted to the University of Cincinnati Division of Graduate Studies in partial fulfillment of the requirements for the degree of

Master of Science

In the Department of Environmental Health of the College of Medicine

8-12-2008 by

Celeste Hemphill B.S., Eastern Kentucky University, 2005

Committee: Roy McKay, Ph.D. (Chair) Glenn Talaska, Ph.D. Paul Succop, Ph.D.

Abstract

This study was conducted to determine the percentage of time the OSHA Rule of

Thumb for respirator cartridge service life agrees with a computer calculated model for CBRN-approved air purifying respirators. Test conditions used and organic vapors evaluated in the OSHA/NIOSH MultiVapor software model were chosen from the NIOSH certification testing criteria for CBRN respirators. Service life predicted from the software model evaluated at concentrations of 2600, 260, 26, and 2.6 ppm was compared to the OSHA Rule of Thumb. When determining service life for

CBRN approved respirators, applying the OSHA Rule of Thumb was found to be most successful at 26 ppm (96.6%). Success rate of the OSHA Rule of Thumb was found to be 93.2% and 94.9% at the concentrations of 260 and 2.6 ppm, respectively.

Statistical analysis of the data indicates the OSHA Rule of Thumb to be acceptable in determining service life for CBRN approved respirators.

ii

iii Acknowledgements

I would like to give my deepest thanks to my advisor Dr. Roy McKay for encouragement and guidance through this project. I would also like to thank my thesis committee members, Dr. Glenn Talaska and Dr. Paul Succop of the University of Cincinnati for their guidance and assistance with this project.

This research was partially by the National Institute for Occupational Health

(NIOSH) University of Cincinnati Education and Research Center Grant #T42-

OH008432-03 and the Powell/Cohrssen Scholarship fund. Without the assistance of this I would not have been able to gain valuable experience at the University of

Cincinnati and conduct this research project.

Lastly I would like to thank my family and friends that supported me as I have worked my way through school.

iv Table of Contents

Abstract…………………………………………………………………………....ii

Acknowledgements……………………………………………………………….iv

Table of Contents………………………………………………………………….v

List of Tables……………………………………………………………………..vi

List of Figures……………………………………………………………………vii

I. Introduction………………………………………………………………..8

II. Methods…………………………………………………………………..13

III. Results……………………………………………………………………15

IV. Conclusions………………………………………………………………22

V. Tables…………………………………………………………………….27

VI. Figures…………………………………………………………………....43

VII. References………………………………………………………………..46

VIII. Appendices……………………………………………………………….48

v List of Tables

1. TIC/TIM Families and TRA…………………………………………………27

2. Canister Test Challenge and Breakthrough Concentrations…………………28

3. Organic Vapors Evaluated in This Study and Corresponding CAS #...... 29

4. NIOSH Certification Testing Conditions…………………………………….31

5. Software Model Cartridge Data……………………………………………...32

6. Exposure Limits……………………………………………………………...33

7. OSHA Rule of Thumb……………………………………………………….34

8. OSHA Rule of Thumb Applicability at 25% Relative Humidity……………35

9. OSHA Rule of Thumb Applicability at 80% Relative Humidity……………36

10. OSHA Rule of Thumb Applicability at Both Relative Humidity’s………….37

11. Summary of OSHA Rule of Thumb Applicability…………………………..38

12. χ2 for OSHA Rule of Thumb at 25% Relative Humidity…………………...39

13. χ2 for OSHA Rule of Thumb at 80% Relative Humidity…………………...40

14. χ2 for OSHA Rule of Thumb at Both Relative Humidity’s Combined…….41

15. Chi Square ( χ2 ) Distribution Table………………………………………….42

vi List of Figures

1. OSHA Rule of Thumb Applicability at 25% Relative Humidity……………43

2. OSHA Rule of Thumb Applicability at 80% Relative Humidity……………44

3. OSHA Rule of Thumb Applicability Comparison at 25% and 80%

Relative Humidity……………………………………………………………45

vii

I. Introduction

The first lines of defense to protect workers from harmful chemical and physical agents encountered in the workplace are engineering and administrative controls.

When engineering and administrative controls are found to not protect the worker, personal protective equipment is used. Use of personal protective equipment in the workplace is regulated by the Occupational Safety and Health Administration

(OSHA). Employers are required to provide an employee a respirator that protects from exposure to harmful airborne contaminants. OSHA’s Respiratory Protection

Standard, 29 CFR 1910.134 states that when respirators are used in the workplace, a written respiratory protection program must be established and implemented by the employer. This program must include procedures for the following: respirator selection, medical evaluations of employees required to wear respirators, fit testing for tight-fitting respirators, proper use of respirators in routine and emergency situations, schedules for respirator maintenance; adequate air quality, quantity, flow of breathing air for atmosphere supplying respirators, training of employees of the respiratory hazards of potential exposure, training of employees in the proper use of respirators, and evaluation for the effectiveness of the program. Once a respirator has been selected, a requirement in the respiratory protection program is the development and implementation of a cartridge change-out schedule for the conditions in which the chosen respirator will be used (OSHA, 2006).

8

A respirator cartridge change-out schedule is used to determine the length of time that a cartridge can be used before being discarded and replaced. Service life is the length of time a cartridge will effectively remove contaminants from the incoming air stream. Calculating the breakthrough time that a contaminant can be detected on the downside of the cartridge is one method that can be used to determine cartridge service life (Plog, 2002). Other methods include: experimental testing, math models, or manufacturer’s recommendations (OSHA, 2006). When using these methods, several factors must be considered to calculate the cartridge service life including: cartridge type, concentration of the contaminant, temperature, humidity, filtering capacity of cartridge, pattern of respirator use, and breathing rate (Plog, 2002). Once all factors have been considered and the service life of the cartridges determined, a change-out schedule can be developed and implemented in a written respiratory protection program. An accurate cartridge change-out schedule must be implemented to ensure that workers are adequately protected from exposure to harmful airborne contaminants in the workplace.

A quick method used to determine the service life of a cartridge is the Rule of Thumb developed by OSHA. This method can be applied to determine the cartridge service life when exposed to chemicals at varying environmental conditions. The Rule of

Thumb consists of four suggestions: (1) if a chemical’s boiling point is above 70ºC and the contaminant concentration is less than 200 parts per million (ppm), service life is generally expected to be 8 hours at a normal work rate; (2) cartridge service life

9 is inversely proportional to work rate; (3) when the concentration is decreased by a factor of 10, the service life is increased by a factor of 5; (4) service life is reduced by

50% when the relative humidity is above 85% (OSHA, 2007). This study will be conducted with the suggestion concerning the concentration. For example, if the service life of a cartridge at 100 ppm is 30 minutes; when the concentration is reduced 10 fold to 10 ppm, the service life can be increased to 150 minutes. The generalizations of the Rule of Thumb are thought to be correct, but service life should be determined in conjunction with other methods such as math models or software programs. OSHA and NIOSH have developed the software program MultiVapor, which is used to determine the cartridge service life. This program allows the user to enter in parameters of the cartridge being evaluated, the environmental conditions in which the cartridge will be used, the contaminant(s) the cartridge will be used against, and the contaminant airborne and breakthrough concentrations. Once all parameters have been entered into the program, an estimated average breakthrough time will be given, along with the minimum and maximum breakthrough time in minutes.

When choosing a respirator, the employer must select and provide one appropriate to protect the worker from the respiratory hazards that are potentially present in the workplace. OSHA’s Respiratory Protection Standard requires all respirators to be certified by The National Institute for Occupational Safety and Health (NIOSH) and used in compliance with the respirator’s certification (OSHA, 2006). Within The

Centers for Disease Control and Prevention (CDC) and in the Department of Health and Human Services (DHHS), NIOSH is the regulatory agency responsible for testing

10 and certifying respirators and cartridges as well as issuing recommendations for the use of respirators (NIOSH, 2007). 42 CFR Part 84, Respiratory Protective Devices, identifies the requirements for certification approval of respirators. Each type of respirator and parts are covered under this standard. Once certified, approved respirators and cartridges are marked with approval labels and markings (NIOSH,

1995).

Prior to 2001, NIOSH standards for respirator certification did not include respirators providing Chemical, Biological, Radiological, and Nuclear (CBRN) protection.

Recent terrorism events in the United States and the world, have led NIOSH to team with several agencies and organizations to develop standards for testing and certifying CBRN respirators to protect from CBRN threats. Agencies involved in the standard development included: National Institute of Standards and Technology

(NIST), Occupational Safety and Health Administration (OSHA), Department of

Homeland Security (DHS), Department of Defense (DOD), National Fire Protection

Association (NFPA), InterAgency Board (IAB), Federal Bureau of Investigation

(FBI), National Institute of Justice (NIJ), and the U.S. Army Research, Development and Engineering Command, Edgewood Chemical Biological Center (RDECOM). In

2001 NIOSH began to publish the first standards for CBRN-certified respirators from these collaborations. CBRN standards have been developed for the following classifications of respirators: full facepiece air purifying respirators (APR), full facepiece air purifying escape respirators (APER), self- contained breathing apparatus

11 (SCBA), self-contained escape respirators, and loose-and tight-fitting powered air purifying respirators (PAPR) (Cloonan, 2007).

In the development of the CBRN respiratory protection standards for full facepiece

APRs, NIOSH developed a list of chemicals used to challenge the cartridge/canister of the respirator. A list of 139 toxic industrial materials (TIMs) and toxic industrial chemicals (TICs) was established and categorized into families. For each of the seven families, a total of eleven test representative agent(s) were selected as the challenge agent. Table 1 lists the families and the test representative agent(s)

(Betsinger, 2007). Each of the eleven challenge agents are used to test against the

CBRN canister at specific test conditions and concentrations. Table 2 lists the canister test challenge concentration and breakthrough concentrations used in the certification testing. Canisters are tested in 15-minute intervals to determine the service life. The following conditions are used when performing the testing: flow rate of 64 liters per minute (LPM); temperature of 25±5° C; 25±5% relative humidity and

80±5% relative humidity (NIOSH, 2008). Upon passing each certification tests, the respirators are approved by NIOSH and given the proper approval labels and markings.

This study will involve calculating the recommended cartridge service life; specifically for Chemical, Biological, Radiological, and Nuclear (CBRN) approved respirators; using the cartridge change-out computer software program developed by

OSHA/NIOSH and comparing these results to results determined by applying the

12 OSHA Rule of Thumb to the NIOSH CBRN certification testing criteria. The OSHA

Rule of Thumb states that for every 10-fold decrease in the airborne contaminant concentration, the cartridge service life can be increased by 5 fold (OSHA, 2007).

Specific contaminants will be chosen and evaluated for comparison at four separate contaminant vapor concentrations using NIOSH certification test conditions. This study will also calculate the shortest and average service life of specific contaminants when the concentration is altered. Concentrations at the Threshold Limit Value

(TLV ®) as set by the American Conference of Governmental Industrial Hygienists

(ACGIH), concentrations above the TLV, and concentrations that are Immediately

Dangerous to Life and Health (IDLH) will be used to determine the service life and compared (ACGIH, 2008).

II. Methods

This study was conducted to determine the percentage of time the OSHA Rule of

Thumb is applicable in determining the cartridge service life for CBRN approved respirators when successively decreasing the airborne concentration of chosen organic solvents from a relatively high concentration to a significantly lower concentration compared to the service life calculated from the OSHA/NIOSH

MultiVapor software program. Documentation by NIOSH of approval standards for

CBRN approved respirators was reviewed to determine the testing requirements and contaminants chosen and evaluated in this study. Table 3 lists the contaminants, along with their corresponding CAS #’s that were evaluated in this study. Testing

13 conditions used during the evaluation were identical to the NIOSH CBRN certification testing conditions. Located in Table 4, the two test conditions used consisted of the same environmental conditions, but using relative humidity at two levels, 25% and 80%.

The MultiVapor software available on the NIOSH website was downloaded for use in this study. Testing conditions and specific contaminants were entered into the software program. Specifications for the type of organic vapor cartridge evaluated in this study are located in Table 5. For this evaluation a carbon weight of 45 grams was chosen and is larger than 26 grams used in a typical organic vapor cartridge. The cartridge bed diameter and depth were determined by using the carbon weight of 45 grams and equivalent to specifications that are used in a cartridge consisting of 26 grams of carbon. Additional cartridge specifications used were preprogrammed parameters in the software model of a typical organic vapor cartridge. After the two test conditions located in Table 4 were established, the organic vapor evaluated was chosen from the preprogrammed list in the software model. The average vapor concentrations used in the contaminant evaluation were 2600, 260, 26, and 2.6 parts per million (ppm). 2600 ppm was chosen because this concentration is used by

NIOSH when certifying CBRN respirators for organic vapors. The remaining concentrations represent progressive 10 fold reductions used by the OSHA Rule of

Thumb approach. After a concentration was established for the chosen organic vapor, the breakthrough concentration was determined. Breakthrough concentration used was 10 ppm; which is the NIOSH certification testing conditions; for the vapor

14 concentrations of 2600, 260, and 26; while a breakthrough concentration of 1 ppm was used for the vapor concentration of 2.6 ppm. Once test conditions and concentrations were inserted, results for the predicted breakthrough time were calculated and recorded. Fifty-nine organic vapors were evaluated at each testing conditions and chosen concentrations. Results were entered into an excel spreadsheet for further evaluation.

Additional data was obtained for the contaminants with TLV and IDLH concentrations. Table 6 lists contaminants and the corresponding TLV and IDLH concentrations. Each contaminant was evaluated at two relative humidity’s of 25 and

80% to simulate the NIOSH certification testing criteria (refer to Table 4) and at the

IDLH, TLV, and at a concentration10 fold below the TLV. The average, minimum and maximum breakthrough time in minutes was recorded for each of the contaminants. Results were entered into an excel spreadsheet for further evaluation.

III. Results

Results for CBRN cartridge service life predicted by the software model are located in data sets 1 thru 8 in Appendix A. Each data set includes the organic vapor evaluated, the test conditions, and the predicted breakthrough time in minutes. In data sets 1 and 8, bold numbers with asterisks indicate when the breakthrough time of

15 minutes was met or exceeded as required by the NIOSH CBRN certification testing requirements. In data sets 2 thru 4 and 6 thru 8, bold numbers with asterisks

15 indicate for this condition, organic vapor and concentration, the OSHA Rule of

Thumb is applicable.

At a concentration of 2600 ppm, NIOSH requires CBRN approved respirators to last at least 15 minutes. When this concentration is decreased 10 fold to 260 minutes, the

OSHA Rule of Thumb allows for a 5 fold increase in service life, thus giving the new service life of 75 minutes. Another 10 fold decrease in concentration to 26 ppm would increase the service life another 5 fold to a time of 375 minutes. Lastly, decreasing the concentration another 10 fold to the lowest concentration evaluated of

2.6 ppm, would increase the service life to 1875 minutes according to the Rule of

Thumb. This is summarized in Table 7.

Concentration for data sets 1 and 5 was 2600 ppm with data set 1 evaluated at 25% relative humidity and data set 5 evaluated at 80% relative humidity. At this concentration and both of the relative humidities evaluated, NIOSH requires CBRN approved respirators to last at least 15 minutes before breakthrough is detected. The bold numbers with asterisks on the data sheets indicate when this time is met or exceeded as predicted by the MultiVapor software program. Data set 1 shows at

2600 ppm and 25% relative humidity, 38 of the 59 organic vapors evaluated were predicted by the software calculator to have an acceptable breakthrough time of 15 minutes. Data set 5 shows at this concentration and at 80% relative humidity, 37 of the 59 organic vapors met this requirement.

16 Data sets 2 and 6 used a concentration of 260 ppm with data set 2 evaluated at 25% relative humidity and data set 6 evaluated at 80% relative humidity. At this concentration, the OSHA Rule of Thumb states that a 5 fold increase to the 15 minute previous service life would give a new service life 75 minutes. The bold numbers with asterisks in the data set indicate when the estimated service life meets or exceeds the new service life of 75 minutes. Table 8 shows at this concentration and 25% relative humidity, 56 of the 59 organic vapors evaluated (94.9%) were predicted by the software calculator to meet or exceed the breakthrough time of 75 minutes. This shows that 94.9% of the time the OSHA Rule of Thumb would be applicable to be used to determine the cartridge service life with the decrease in concentration. Table

9 shows at this concentration and 80% relative humidity 54 of the 59 organic vapors

(91.5%) acceptably met or exceeded the 75 minute breakthrough time.

Another 10 fold decrease was applied to the concentration for data sets 3 and 7. At

26 ppm, with data set 3 evaluated at 25% relative humidity and data set 7 evaluated at

80% relative humidity, a 5 fold increase to the previous service life of 75 minutes would increase the time to 375 minutes, when applying the OSHA Rule of Thumb.

The bold numbers with asterisks located in data sets 3 and 7 indicate when breakthrough time was acceptably met or exceeded. Table 8 shows at this concentration and 25% relative humidity, 57 of 59 organic vapors evaluated (96.6%) were predicted by the software calculator to acceptably meet or exceed the breakthrough time of 375 minutes. Table 9 also shows at this concentration and

17 relative humidity of 80%, 57 of the 59 organic vapors (96.6%) met this breakthrough time.

Concentration for data sets 4 and 8 was 2.6 ppm with data set 4 evaluated at 25% relative humidity and data set 8 evaluated at 80% relative humidity. This was the lowest concentration used in evaluating the OSHA Rule of Thumb against the software model estimated service life. Service life at this concentration would be

1875 minutes when the OSHA Rule of Thumb is applied. The bold numbers with the asterisks in the data set indicate when the estimated breakthrough time met or exceeded this new requirement. At 2.6 ppm and 25 % relative humidity, Table 8 shows 57 of the 59 organic vapors evaluated (96.6%) were predicted by the software calculator to meet or exceeded the breakthrough time of 1875 minutes. Table 9 shows that this concentration and 80% relative humidity, 55 of 59 organic vapors

(93.2%) successfully met or exceeded this breakthrough time.

Data sets 2 thru 4 each had a different concentration, but each set used a relative humidity of 25% for evaluation. Combined results for the applicability of the OSHA

Rule of Thumb when compared to the software model predicted service life are located in Tables 8 and 11. Table 8 shows that 170 of the 177 organic vapors evaluated (96.0%) were predicted by the software model to successfully meet or exceed the service life when compared to the OSHA Rule of Thumb. Figure 1 graphically shows each concentration and the applicability of the OSHA Rule of

18 Thumb for data sets 2 thru 4. Data sets 6 thru 8 show different concentration points for each, but were evaluated at 80% relative humidity. Combined results for these evaluations are located in Tables 9 and 11. Table 9 shows that 166 of the 177 organic vapors evaluated (93.8%) were predicted by the software model to successfully meet or exceed the service life when compared to the OSHA Rule of Thumb. Figure 2 graphically shows each concentration and the applicability of the OSHA Rule of

Thumb for data sets 5 to 8. Tables 10 and 11 show a comparison of the combined results for data sets evaluated at 25% and 80% relative humidity. Table 10 shows that at 260 ppm, 110 of 118 times (93.2%) the acceptable breakthrough time was met or exceeded when compared to the OSHA Rule of Thumb. For concentrations of 26 ppm and 2.6 ppm, the predicted software calculator breakthrough time acceptably met or exceeded the breakthrough time when compared to the OSHA Rule of Thumb for

114 and 112 times each of 118 respectively (96.6% and 94.9%). Figure 3 shows a representation of the OSHA Rule of Thumb applicability compared at 25% and 80% relative humidity at the concentrations of 260, 26 and 2.6 ppm. Table 11 shows for data sets 2 thru 4 and 6 thru 8, 336 of the 354 evaluations (94.9%) were predicted by the software model to successfully meet or exceed the service life when compared to the OSHA Rule of Thumb.

Tables 12, 13 and 14 show results for chi square statistics. This statistic was used to test the null hypothesis that the OSHA Rule of Thumb is always applicable to be used to determine the service life for CBRN approved respirators when airborne concentrations for specific organic vapors are successively decreased and compared

19 to the OSHA/ NIOSH MultiVapor software program. Table 12 shows that the χ2 calculated for the concentrations evaluated at 25% relative humidity was 0.29, while

Table 13 shows that the χ2 for the concentrations evaluated at 80% relative humidity was 0.76. Table 14 shows the combined results for concentrations at both humidities with a calculated χ2 value of 0.99. Table 15 displays the chi squared statistic distribution table. When using an alpha level of 0.05 and 2 degrees of freedom chosen from a table using three rows and two columns; the χ2 value in the distribution table is 5.991. At this alpha level the calculated chi square statistic for concentrations evaluated at 25% relative humidity, concentrations evaluated at 80% relative humidity, and the combined relative humidities are each below this level and would thus be accepted.

Results for additional evaluations of the estimated service life calculated by the software model for substances at the IDLH, TLV, and concentrations successively lower than the TLV are located in Appendix A in data sets 9 and 10. Each data set includes the test conditions, organic vapor evaluated, and the minimum, maximum, and estimated breakthrough time in minutes. Estimated service life for contaminants evaluated at the IDLH concentration and at 25% relative humidity range from 29 to

7159 minutes. Estimated service life for contaminants evaluated at the IDLH concentration and at 80% relative humidity range from 25 to 4425 minutes. When the service life was evaluated for substance at the TLV, results shown in data set 9 at the listed TLV and at 25% relative humidity, estimated service life ranged from 242

20 to 478,110 minutes. Data set 10 shows that at the TLV and at 80% humidity, the estimated service life ranged from 175 to 342,826 minutes.

Data sets 1A and 5A, located in Appendix A, show the predicted service life obtained from the software program evaluated at 2600 ppm with data set 1A evaluated at 25% relative humidity and data sets 5 evaluated at 80% relative humidity. Each data set includes the test conditions, concentration, organic vapor evaluated, and the breakthrough time in minutes listed from shortest to longest. The bold numbers with asterisks in the data set indicate when the breakthrough time of 15 minutes required from the NIOSH CBRN certification testing criteria was met or exceeded. Data sets

2A thru 4A and 6A thru 8A, located in Appendix A, include the test conditions, concentration, organic vapor evaluated, and the breakthrough time in minutes listed from shortest to longest. The bold numbers with asterisks in the data set indicate when the estimated service life meets or exceeds the breakthrough time predicted when applying the OSHA Rule of Thumb.

In data sets 1A and 5A, the organic vapor with the shortest breakthrough time at 2600 ppm was hexaethyl tetraphosphate with a predicted time of zero minutes. The next two organic vapors with the shortest breakthrough time at 2600 ppm, as shown in data sets 1A and 5A, were methyl parathion and o-chlorobenzylidene malonitrile.

Data set 4A shows that the ranking of the three organic vapors with the shortest breakthrough time changes, when the concentration was decreased to 2.6 ppm. The ranking of hexaethyl tetraphosphate, methyl parathion and o-chlorobenzylidene

21 malonitrile are shown in data set 4A as 16 th , 39 th , and 50 th respectively. Data set 8A shows at 2.6 ppm and 80% relative humidity, ranking for hexaethyl tetraphosphate, methyl parathion and o-chlorobenzylidene malonitrile was found to be 17 th , 40 th , and

51 st respectively. Data sets 1A and 5A show chloroacetonitrile had the longest predicted breakthrough time, preceded by methanesulfonyl chloride. When the concentration was decreased to 2.6 ppm and 25% relative humidity, data set 4A shows that ranking was found to be 4 th and 25 th for chloroacetonitrile and methanesulfonyl chloride, respectively. A similar ranking was found in data set 8A for chloroacetonitrile and methanesulfonyl chloride, but at 2.6 ppm and 80% relative humidity the ranking was found to be 4 th and 24 th , respectively.

IV. Conclusions

When determining the service life of CBRN approved respirators, NIOSH certification testing is the basis for determination of expected service life. This certification states that the service life for CBRN approved respirators when exposed to organic vapors at 2600 ppm is 15 minutes. This study shows that the OSHA Rule of Thumb is most applicable to be used in determining a change-out schedule, specifically for CBRN approved respirators, at the concentration of 26 ppm evaluated at relative humidity’s of 25% and 80%. This is a 100 fold decrease from the NIOSH test certification concentration. The success rate at 26 ppm and 25% relative humidity was 96.6%, which is the same success rate 80% relative humidity at the same concentration. Decreasing the concentration another 10 fold to 2.6 ppm, the

OSHA Rule of Thumb decreased in applicability at 80% relative humidity while

22 being the same for 25% relative humidity. At 2.6 ppm and at 80% relative humidity, success rate when applying the OSHA Rule of Thumb was found to be 93.2%, which is 3.4% less applicable than at 26 ppm. Applicability of the rule of thumb was the lowest at the concentration of 260 ppm. The success rate at this concentration and

25% relative humidity was 94.9%, while there was a success rate of 91.5% at 260 ppm and 80%. The OSHA Rule of Thumb is used to further determine the service life once the concentration is lower than the testing criteria, since at this concentration the OSHA Rule of Thumb is not applied.

Overall, this study found that the OSHA Rule of Thumb was applicable 96.0% of the time when compared to results of estimated service life with the three concentrations combined and 25% relative humidity. When the three concentrations were combined at 80% relative humidity, the OSHA Rule of Thumb was found to be applicable

93.8% of the time when compared to the software model. The OSHA Rule of Thumb was found to be applicable 94.9% of the time when the three concentrations and both relative humidity’s were combined.

The chi square statistic was calculated to test the null hypothesis that the OSHA Rule of Thumb is always applicable to determine cartridge service life for CBRN approved respirators when compared to the OSHA/ NIOSH MultiVapor software program. The null hypothesis was accepted each of the three times that it was calculated. The obtained chi square values for the concentrations at 25% relative humidity, at 80%

23 relative humidity, and at both relative humidities combined, were below the 0.05 alpha level of 5.991 at 2 degrees of freedom. Thus, the OSHA Rule of Thumb is always applicable to be used to determine service life for CBRN approved respirators when compared to the OSHA/NIOSH MultiVapor software. These results are entirely due to the departures from expectation at 2600 ppm.

Data sets 1A and 5A show that for the organic vapor hexaethyl tetraphosphate evaluated at both test conditions and at 2600 ppm, the predicted breakthrough time was found to be zero minutes. This implies that the cartridge would not protect against this organic vapor. There is the question to why this may be so low. This may be due to the fact that the specifications of the cartridge evaluated in the software program may not be true to the specifications of a typical certified CBRN canister.

Further evaluation with changing the adsorption potential for benzene in the cartridge parameters in the software model, did predict a longer breakthrough time at 2600 ppm for hexaethyl tetraphosphate. Further evaluation using the true parameters of CBRN- approved respirator data may give different results.

When the predicted breakthrough times were ranked from shortest to longest predicted time at each of the concentrations evaluated, drastic changes were found.

The three organic vapors with the shortest time at 2600 ppm were found to be ranked

16 th , 39 th , and 50 th when evaluated at 2.6 ppm and 25% relative humidity and also found to be ranked 17 th , 40 th , and 51 st when evaluated at 2.6 ppm and 80% relative

24 humidity. Another drastic change was found when looking at the two organic vapors with the longest predicted breakthrough times at 2600 ppm. When evaluated at 2.6 ppm and 25% relative humidity the new ranking for predicted breakthrough time was found to be 4 th and 25 th while they were next found to be ranked at 4 th and 24 th when evaluated at 2.6 ppm and 80% relative humidity. There may be such a drastic change in the ranking due to the specifications of the cartridge entered into the program.

Since breakthrough time does depend on the adsorption capacity and adsorption rate, entering the true CBRN-approved canister parameters into the computer model may yield different results. Also, both adsorption parameters depend on the concentration, but do so in differing ways. This may cause the drastic changes in the ranking of the organic vapors evaluated at the four concentrations. Future evaluations of the software program should be conducted to investigate this question.

This study does raise the question of the adequacy of cyclohexane as the test challenge agent when certifying CBRN respirators. Data sets 1A and 5A show that the predicted breakthrough time for 22 organic vapors were lower than that of cyclohexane. Cyclohexane was chosen as the representative test agent because of its high vapor pressure and was determined that each contaminant in the organic vapor family would meet the breakthrough time of 15 minutes at the challenge concentration of 2600 ppm. However, this was not found to be the case when these organic vapors were entered into the MultiVapor software program and evaluated at each of the CBRN certification test conditions. This study found that cyclohexane may not be the most appropriate representative test agent for the organic vapor family

25 for CBRN certification. Also, there may need to be more than one test agent used for organic vapors when testing to certify a CBRN respirator.

One of the limitations of this study was that the specifications on the canister evaluated in the MultiVapor software program may not accurately portray the true specifications of a typical CBRN approved canister. The parameters were determined by using the data of a typical organic vapor cartridge and increasing the carbon weight. The bed diameter and bed depth were calculated using the new carbon weight and being equivalent to specifications of a typical organic vapor cartridge carbon weight. Future evaluations using the true specifications of a typical CBRN approved canister should be conducted to better evaluate the software program and the applicability of the OSHA Rule of Thumb. Parameters such as the bed diameter, bed depth, carbon weight, adsorption potential, micropore volume, carbon granule average diameter, affinity coefficient for water, and preconditioned relative humidity specifically for CBRN-approved respirator canisters should be entered into the computer model to give a more accurate breakthrough time. A strength of this study is that the NIOSH testing conditions that are used in the approval process for CBRN respirators was accurately evaluated. Both sets of the testing conditions that are used were evaluated separately in this study.

26

V. Tables

Table 1: TIC/TIM Families and TRA umber of Family Test Representative Agent Compounds 61 Organic vapor family Cyclohexane 32 Acid gas family SO 2, H 2S, CNCl, COCl 2, HCN 4 Base gas family Ammonia 4 Hydride Family Phosphine 5 Nitrogen oxide family Nitrogen Dioxide 1 Formaldehyde family Formaldehyde 32 Particulate family DOP

27 Table 2: Canister Test Challenge and Breakthrough Concentrations Test Concentration Breakthrough Concentration (ppm) (ppm) Ammonia 2500 12.5 Cyanogen Chloride 300 2 Cyclohexane 2600 10 Formaldehyde 500 1 Hydrogen Cyanide 940 4.7 (1) Hydrogen Sulfide 1000 5.0 (2) Nitrogen Dioxide 200 1 ppm NO 2 or 25 ppm NO Phosgene 250 1.25 Phosphine 300 0.3 Sulfur Dioxide 1500 5 (1) Sum of HCN and C 2N2 (2) Nitrogen Dioxide breakthrough is monitored for both NO 2 and NO. The breakthrough is determined by which quantity, NO 2 or NO, reaches breakthrough first.

28 Table 3: Organic Vapors Evaluated in This Study and Corresponding CAS # Substance CAS # 1. Acetone cyanohydrin 75-86-5 2. Acrylonitrile 107-13-1 3. Allyl alcohol 107-18-6 4. Allyl chlorocarbonate 2937-50-0 5. Bromoacetone 598-31-2 6. Chloroacetone 78-95-5 7. Chloroacetonitrile 107-14-2 8. Chloroacetyl chloride 79-04-9 9. Chloropicrin 76-06-2 10. Crotonaldehyde 4170-30-3 11. Cyclohexane 110-82-7 12. Cyclohexyl methylphosphonate 1932-60-1 13. Dibenz-(b,f)-1,4-oxazepine 257-07-8 14. Diketene 674-82-8 15. Dimethyl sulfate 77-78-1 16. Diphenylchloroarsine 712-48-1 17. Diphenylcyanoarsine 23525-22-6 18. Diphosgene 503-38-8 19. Distilled mustard 505-60-2 20. Ethyl chloroformate 541-41-3 21. Ethyl chlorothioformate 2941-64-2 22. Ethyl phosphonothioicdichloride 993-43-1 23. Ethyl phosphorodichloridate 1498-51-7 24. Ethylene dibromide 106-93-4 25. Hexachlorocyclopentadiene 77-47-4 26. Hexaethyl tetraphosphate 757-58-4 27. Iso-butyl chloroformate 543-27-1 28. Iso-propyl chloroformate 108-23-6 29. Lewisite 541-25-3 30. Methanesulfonyl chloride 124-63-0 31. Methyl orthosilicate 681-84-5 32. Methyl parathion 298-00-0 33. Methyl phosphonic dichloride 676-97-1 34. Mustard, lewisite mixture none 35. Nitrogen mustard HN-1 538-07-8

29 36. Nitrogen mustard HN-2 51-75-2 37. Nitrogen mustard HN-3 555-77-1 38. n-propyl chloroformate 109-61-5 39. o-chlorobenzylidene malononitrile 2698-41-1

40. o-ethyl-s-(2isopropyaminoethyl)- unknown methyl phosphothiolate

41. Parathion 56-38-2 42. Perchloromethyl mercaptan 594-42-3 43. Phenyl mercapatan 108-98-5 44. Phenylcarbylamine chloride 622-44-6

45. Phenyldichloroarsine 696-28-6 46. Phosgene oxime 1794-86-1 47. Phosphorous oxychloride 1025-87-3 48. Sarin 107-44-8 49. Sec-butyl chloroformate 17462-58-7 50. Soman 96-64-0 51. Tabun 77-81-6 52. Tert-octyl mercaptan 141-59-3 53. Tetraethyl dithiopyrophosphate 3689-24-5

54. Tetraethyl lead 78-00-2 55. Tetramethyl lead 75-74-1 56. Tetranitromethane 509-14-8 57. Trimethoxysilane 2487-90-3 58. Trimethylacetyl chloride 3282-30-2 59. VX 50782-69-9

30 Table 4: IOSH Certification Testing Conditions Condition #1 Condition #2 Temperature 25°C 25°C Relative Humidity 25% 80% Flow Rate 64 LPM 64 LPM umber of Cartridges 1 1 Atmospheric Pressure 1.00 atm 1.00 atm

31 Table 5: Software Model Cartridge Data Parameter Value Bed Diameter (cm) 7.45 Bed Depth (cm) 2.32 Carbon Weight (g) per 45 Cartridge Micropore Volume (cm 3/g) 0.454 Preconditioned Relative 20 Humidity (%) Carbon Granule Average 0.11 Diameter (cm) Adsorption Potential for 18.00 Benzene (KJ/mol) Affinity Coefficient for Water 0.060

32 Table 6: Exposure Limits TLV IDLH Substance (ppm) (ppm) Acrylonitrile 2 85 Allyl alcohol 0.5 20 Chloropicrin 0.1 2 Crotonaldehyde None 50 Cyclohexane 100 1300 Perchloromethyl mercaptan 0.1 10 Tetranitromethane 0.005 4 Phenyl mercaptan 0.1 N.D. Dimethyl sulfate 0.1 7 Chloroacetyl chloride 0.05 N.D. N.D.=not determined

33 Table 7: OSHA Rule of Thumb Concentration OSHA Rule of Thumb (ppm) (minutes) 2600 15 260 75 26 375 2.6 1875

34 Table 8: OSHA Rule of Thumb Applicability at 25% Relative Humidity Concentration Yes o Total % Applicable (ppm) 260 56 3 59 94.9 26 57 2 59 96.6 2.6 57 2 59 96.6 Total 170 7 177 96.0

35 Table 9: OSHA Rule of Thumb Applicability at 80% Relative Humidity Concentration Yes o Total % Applicable (ppm) 260 54 5 59 91.5 26 57 2 59 96.6 2.6 55 4 59 93.2 Total 166 11 177 93.8

36 Table 10: OSHA Rule of Thumb Applicability at Both Relative Humidities Concentration Yes o Total % Applicable (ppm) 260 110 8 118 93.2 26 114 4 118 96.6 2.6 112 6 118 94.9 Total 336 18 354 94.9

37 Table 11: Summary of OSHA Rule of Thumb Applicability Yes o Total 25% RH 170 7 177 80% RH 166 11 177 Total 336 18 354 94.9% 5.1%

38 Table 12: χ2 for OSHA Rule of Thumb Results at 25 % Relative Humidity Concentration Observed Expected |OE| (OE) 2 (OE) 2/E (ppm) (O) (E) 260 56 59 3 9 0.15 26 57 59 2 4 0.07 2.6 57 59 2 4 0.07 Total χ2=0.29

39 Table 13: χ2 for OSHA Rule of Thumb Results at 80 % Relative Humidity Concentration Observed Expected |OE| (OE) 2 (OE) 2/E (ppm) (O) (E) 260 54 59 5 25 0.42 26 57 59 2 4 0.07 2.6 55 59 4 16 0.27 Total χ2=0.76

40 Table 14: χ2 for OSHA Rule of Thumb at Both Relative Humidities Combined Concentration Observed Expected |OE| (OE) 2 (OE) 2/E (ppm) (O) (E) 260 110 118 8 64 0.54 26 114 118 4 16 0.14 2.6 112 118 6 36 0.31 Total χ2=0.99

41 Table 15: Chi Square ( χ2) Distribution Table Alpha 0.5 0.10 0.05 0.01 df 1 0.455 2.706 3.841 6.635 2 1.386 4.605 5.991 9.210 3 2.366 6.251 7.815 11.345 4 3.357 7.779 9.488 13.277 5 4.351 9.236 11.070 15.086 df=degrees of freedom

42 VI. Figures

60

50

40 Yes 30 No 20

10 Number Number of Organic Vapors 0 260 26 2.6 Concentration (ppm)

Figure 1: OSHA Rule of Thumb Applicability at 25% Relative Humidity

43 60

50

40 Yes 30 No 20

10 Number Number of Organic Vapors 0 260 26 2.6 Concentration (ppm)

Figure 2: OSHA Rule of Thumb Applicability at 80% Relative Humidity

44 60 55 50 45 40 35 25% Relative Humidity 30 25 80% Relative Humidity

Applicable 20 15 10

Number Number of Organic Vapors 5 0 260 26 2.6 Concentration (ppm)

Figure 3: OSHA Rule of Thumb Applicability Comparison at 25% and 80% Relative Humidity

45 VII. References

American Conference of Governmental Industrial Hygienists (ACGIH) : 2008 Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices . ACGIH ®, Cincinnati, Ohio (2008).

Betsinger CIH, Geoff. : An Overview of IOSH CBR Respiratory Protection Standards. 3M JobHealth Highlights. Vol. 25 No. 7: 1-8. (November 2007).

Cloonan, Terrance K., Szalajada, Jonathon V. : IOSHCertified CBR Respirators: Responders’ First Line of Respiratory Protection. The Synergist. Vol. 1 No. 8: 43-47. (September 2007).

ational Institute for Occupational Safety and Health (IOSH): IOSH Pocket Guide to Chemical Hazards , DHHS (NIOSH) Pub. No.2005-149. NIOSH, Cincinnati, Ohio (2006).

ational Institute for Occupational Safety and Health (IOSH): Respirators. http://www.cdc.gov/niosh/npptl/topics/respirators/ . (accessed 12/7/2007).

ational Institute for Occupational Safety and Health (IOSH): Respiratory Protection . Title 42, CFR, Part 84. U.S. Government Printing Offices, Washington, D.C (1995).

ational Institute for Occupational Safety and Health (IOSH): Statement of Standard for Full Facepiece Air Purifying Respirators (APR). http://www.cdc.gov/niosh/npptl/standardsdev/cbrn/apr/standard/aprstd-a.html . (accessed 2/17/2008).

ational Institute for Occupational Safety and Health (IOSH)/The ational Personal Protective Technology Laboratory (PPTL): MultiVapor Version 2.1.3. http://www.cdc.gov/niosh/npptl/multivapor/multivapor.html . (accessed 1/2/2008).

46

Occupational Safety and Health Administration (OSHA): Respiratory Protection . Title 29, CFR, Part 1910.134. U.S. Government Printing Offices, Washington, D.C (2006).

Occupational Safety and Health Administration (OSHA): Rule of Thumb . http://www.osha.gov/SLTC/etools/respiratory/rule_of_thumb/rule_of_thumb.html . (accessed 12/5/2007).

Plog, Barbara A., Quinlan Patricia J, : Fundamentals of Industrial Hygiene. 5 th Edition , National Safety Council. pgs. 668, 694-695, (2002).

47 VIII. Appendices

Appendix A. Data Sets

48 Software Model Data Set 1 Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2600 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 25* Acrylonitrile 17* Allyl alcohol 27* Allyl chlorocarbonate 19* Bromoacetone 27* Chloroacetone 25* Chloroacetonitrile 34* Chloroacetyl chloride 30* Chloropicrin 21* Crotonaldehyde 21* Cyclohexane 16* Cyclohexyl methylphosphonate 12 Dibenz-(b,f)-1,4-oxazepine 11 Diketene 28* Dimethyl sulfate 24* Diphenylchloroarsine 8 Diphenylcyanoarsine 8 Diphosgene 19* Distilled mustard 17* Ethyl chloroformate 21* Ethyl chlorothioformate 22* Ethyl phosphonothioicdichloride 20* Ethyl phosphorodichloridate 19* Ethylene dibromide 26* Hexachlorocyclopentadiene 13 Hexaethyl tetraphosphate 0 Iso-butyl chloroformate 17* Iso-propyl chloroformate 18* Lewisite 21* Methanesulfonyl chloride 31* Methyl orthosilicate 14 Methyl parathion 5 Methyl phosphonic dichloride 26* Mustard, lewisite mixture 20* Nitrogen mustard HN-1 14 Nitrogen mustard HN-2 16* Nitrogen mustard HN-3 11 n-propyl chloroformate 18* o-chlorobenzylidene malononitrile 5 o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 8 Parathion 7 Perchloromethyl mercaptan 21* Phenyl mercapatan 23* Phenylcarbylamine chloride 17* Phenyldichloroarsine 15* Phosgene oxime 28* Phosphorous oxychloride 10 Sarin 18* Sec-butyl chloroformate 17* Soman 12 Tabun 13 Tert-octyl mercaptan 13 Tetraethyl dithiopyrophosphate 6 Tetraethyl lead 11 Tetramethyl lead 16* Tetranitromethane 18* Trimethoxysilane 14 Trimethylacetyl chloride 16* VX 7

49 Software Model Data Set 2 Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 260 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 271* Acrylonitrile 58 Allyl alcohol 154* Allyl chlorocarbonate 157* Bromoacetone 238* Chloroacetone 187* Chloroacetonitrile 212* Chloroacetyl chloride 286* Chloropicrin 167* Crotonaldehyde 158* Cyclohexane 112* Cyclohexyl methylphosphonate 148* Dibenz-(b,f)-1,4-oxazepine 139* Diketene 210* Dimethyl sulfate 261* Diphenylchloroarsine 114* Diphenylcyanoarsine 110* Diphosgene 179* Distilled mustard 209* Ethyl chloroformate 152* Ethyl chlorothioformate 193* Ethyl phosphonothioicdichloride 206* Ethyl phosphorodichloridate 210* Ethylene dibromide 216* Hexachlorocyclopentadiene 161* Hexaethyl tetraphosphate 17 Iso-butyl chloroformate 159* Iso-propyl chloroformate 151* Lewisite 236* Methanesulfonyl chloride 282* Methyl orthosilicate 134* Methyl parathion 78* Methyl phosphonic dichloride 247* Mustard, lewisite mixture 227* Nitrogen mustard HN-1 165* Nitrogen mustard HN-2 185* Nitrogen mustard HN-3 145* n-propyl chloroformate 152* o-chlorobenzylidene malononitrile 97* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 108* Parathion 93* Perchloromethyl mercaptan 212* Phenyl mercapatan 242* Phenylcarbylamine chloride 193* Phenyldichloroarsine 190* Phosgene oxime 235* Phosphorous oxychloride 48 Sarin 180* Sec-butyl chloroformate 160* Soman 143* Tabun 168* Tert-octyl mercaptan 135* Tetraethyl dithiopyrophosphate 79* Tetraethyl lead 131* Tetramethyl lead 148* Tetranitromethane 167* Trimethoxysilane 102* Trimethylacetyl chloride 135* VX 86*

50 Software Model Data Set 3 Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 26 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 2275* Acrylonitrile 181 Allyl alcohol 653* Allyl chlorocarbonate 1086* Bromoacetone 1699* Chloroacetone 1081* Chloroacetonitrile 919* Chloroacetyl chloride 2566* Chloropicrin 1150* Crotonaldehyde 855* Cyclohexane 738* Cyclohexyl methylphosphonate 1696* Dibenz-(b,f)-1,4-oxazepine 1679* Diketene 1200* Dimethyl sulfate 2185* Diphenylchloroarsine 1453* Diphenylcyanoarsine 1420* Diphosgene 1498* Distilled mustard 2285* Ethyl chloroformate 902* Ethyl chlorothioformate 1515* Ethyl phosphonothioicdichloride 1956* Ethyl phosphorodichloridate 1965* Ethylene dibromide 1543* Hexachlorocyclopentadiene 1825* Hexaethyl tetraphosphate 468* Iso-butyl chloroformate 1320* Iso-propyl chloroformate 1070* Lewisite 2345* Methanesulfonyl chloride 1976* Methyl orthosilicate 1104* Methyl parathion 1167* Methyl phosphonic dichloride 1926* Mustard, lewisite mixture 2325* Nitrogen mustard HN-1 1775* Nitrogen mustard HN-2 1922* Nitrogen mustard HN-3 1771* n-propyl chloroformate 1068* o-chlorobenzylidene malononitrile 1437* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 1343* Parathion 1194* Perchloromethyl mercaptan 1870* Phenyl mercapatan 2237* Phenylcarbylamine chloride 2054* Phenyldichloroarsine 2180* Phosgene oxime 1587* Phosphorous oxychloride 264 Sarin 1577* Sec-butyl chloroformate 1400* Soman 1529* Tabun 1937* Tert-octyl mercaptan 1313* Tetraethyl dithiopyrophosphate 1018* Tetraethyl lead 1429* Tetramethyl lead 1264* Tetranitromethane 1343* Trimethoxysilane 704* Trimethylacetyl chloride 978* VX 1070*

51 Software Model Data Set 4 Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2.6 ppm Breakthrough Concentration: 1 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 12,859* Acrylonitrile 182 Allyl alcohol 1445* Allyl chlorocarbonate 5252* Bromoacetone 8259* Chloroacetone 3979* Chloroacetonitrile 2131* Chloroacetyl chloride 19,372* Chloropicrin 5584* Crotonaldehyde 2935* Cyclohexane 3232* Cyclohexyl methylphosphonate 15,362* Dibenz-(b,f)-1,4-oxazepine 16,743* Diketene 4298* Dimethyl sulfate 12,353* Diphenylchloroarsine 15,316* Diphenylcyanoarsine 15,144* Diphosgene 9327* Distilled mustard 19,807* Ethyl chloroformate 3492* Ethyl chlorothioformate 8604* Ethyl phosphonothioicdichloride 14,667* Ethyl phosphorodichloridate 13,744* Ethylene dibromide 7793* Hexachlorocyclopentadiene 16,969* Hexaethyl tetraphosphate 6256* Iso-butyl chloroformate 8128* Iso-propyl chloroformate 5341* Lewisite 18,478* Methanesulfonyl chloride 8999* Methyl orthosilicate 6778* Methyl parathion 13,501* Methyl phosphonic dichloride 10,486* Mustard, lewisite mixture 18,912* Nitrogen mustard HN-1 15,208* Nitrogen mustard HN-2 15,705* Nitrogen mustard HN-3 17,377* n-propyl chloroformate 5292* o-chlorobenzylidene malononitrile 16,765* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 13,604* Parathion 12,583* Perchloromethyl mercaptan 12,716* Phenyl mercapatan 16,112* Phenylcarbylamine chloride 17,785* Phenyldichloroarsine 20,531* Phosgene oxime 7079* Phosphorous oxychloride 790 Sarin 10,004* Sec-butyl chloroformate 9268* Soman 12,932* Tabun 17,471* Tert-octyl mercaptan 10,135* Tetraethyl dithiopyrophosphate 10,727* Tetraethyl lead 12,836* Tetramethyl lead 8277* Tetranitromethane 7986* Trimethoxysilane 3213* Trimethylacetyl chloride 5128* VX 11,044*

52 Software Model Data Set 5 Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2600 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 25* Acrylonitrile 15* Allyl alcohol 28* Allyl chlorocarbonate 18* Bromoacetone 27* Chloroacetone 24* Chloroacetonitrile 32* Chloroacetyl chloride 29* Chloropicrin 20* Crotonaldehyde 22* Cyclohexane 15* Cyclohexyl methylphosphonate 11 Dibenz-(b,f)-1,4-oxazepine 10 Diketene 27* Dimethyl sulfate 24* Diphenylchloroarsine 8 Diphenylcyanoarsine 7 Diphosgene 19* Distilled mustard 16* Ethyl chloroformate 19* Ethyl chlorothioformate 21* Ethyl phosphonothioicdichloride 20* Ethyl phosphorodichloridate 19* Ethylene dibromide 25* Hexachlorocyclopentadiene 13 Hexaethyl tetraphosphate 0 Iso-butyl chloroformate 17* Iso-propyl chloroformate 17* Lewisite 21* Methanesulfonyl chloride 31* Methyl orthosilicate 14 Methyl parathion 4 Methyl phosphonic dichloride 26* Mustard, lewisite mixture 19* Nitrogen mustard HN-1 14 Nitrogen mustard HN-2 16* Nitrogen mustard HN-3 10 n-propyl chloroformate 18* o-chlorobenzylidene malononitrile 5 o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 8 Parathion 6 Perchloromethyl mercaptan 21* Phenyl mercapatan 23* Phenylcarbylamine chloride 16* Phenyldichloroarsine 14 Phosgene oxime 27* Phosphorous oxychloride 8 Sarin 18* Sec-butyl chloroformate 16* Soman 12 Tabun 12 Tert-octyl mercaptan 13 Tetraethyl dithiopyrophosphate 5 Tetraethyl lead 11 Tetramethyl lead 15* Tetranitromethane 18* Trimethoxysilane 14 Trimethylacetyl chloride 15* VX 6

53 Software Model Data Set 6 Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 260 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 271* Acrylonitrile 41 Allyl alcohol 150* Allyl chlorocarbonate 132* Bromoacetone 212* Chloroacetone 157* Chloroacetonitrile 169* Chloroacetyl chloride 264* Chloropicrin 141* Crotonaldehyde 132* Cyclohexane 88* Cyclohexyl methylphosphonate 148* Dibenz-(b,f)-1,4-oxazepine 135* Diketene 175* Dimethyl sulfate 253* Diphenylchloroarsine 105* Diphenylcyanoarsine 100* Diphosgene 163* Distilled mustard 209* Ethyl chloroformate 123* Ethyl chlorothioformate 173* Ethyl phosphonothioicdichloride 201* Ethyl phosphorodichloridate 206* Ethylene dibromide 187* Hexachlorocyclopentadiene 160* Hexaethyl tetraphosphate 14 Iso-butyl chloroformate 145* Iso-propyl chloroformate 129* Lewisite 234* Methanesulfonyl chloride 258* Methyl orthosilicate 119* Methyl parathion 64 Methyl phosphonic dichloride 230* Mustard, lewisite mixture 226* Nitrogen mustard HN-1 165* Nitrogen mustard HN-2 185* Nitrogen mustard HN-3 141* n-propyl chloroformate 129* o-chlorobenzylidene malononitrile 80* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 104* Parathion 86* Perchloromethyl mercaptan 200* Phenyl mercapatan 235* Phenylcarbylamine chloride 193* Phenyldichloroarsine 188* Phosgene oxime 224* Phosphorous oxychloride 33 Sarin 181* Sec-butyl chloroformate 147* Soman 143* Tabun 166* Tert-octyl mercaptan 129* Tetraethyl dithiopyrophosphate 73 Tetraethyl lead 131* Tetramethyl lead 131* Tetranitromethane 150* Trimethoxysilane 99* Trimethylacetyl chloride 113* VX 82*

54 Software Model Data Set 7 Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 26 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 2288* Acrylonitrile 119 Allyl alcohol 571* Allyl chlorocarbonate 820* Bromoacetone 1335* Chloroacetone 809* Chloroacetonitrile 643* Chloroacetyl chloride 2197* Chloropicrin 870* Crotonaldehyde 655* Cyclohexane 531* Cyclohexyl methylphosphonate 1696* Dibenz-(b,f)-1,4-oxazepine 1674* Diketene 878* Dimethyl sulfate 1885* Diphenylchloroarsine 1409* Diphenylcyanoarsine 1364* Diphosgene 1238* Distilled mustard 2247* Ethyl chloroformate 655* Ethyl chlorothioformate 1213* Ethyl phosphonothioicdichloride 1779* Ethyl phosphorodichloridate 1769* Ethylene dibromide 1192* Hexachlorocyclopentadiene 1816* Hexaethyl tetraphosphate 396* Iso-butyl chloroformate 1083* Iso-propyl chloroformate 820* Lewisite 2200* Methanesulfonyl chloride 1570* Methyl orthosilicate 895* Methyl parathion 1083* Methyl phosphonic dichloride 1587* Mustard, lewisite mixture 2220* Nitrogen mustard HN-1 1722* Nitrogen mustard HN-2 1834* Nitrogen mustard HN-3 1769* n-propyl chloroformate 812* o-chlorobenzylidene malononitrile 1290* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 1332* Parathion 1156* Perchloromethyl mercaptan 1607* Phenyl mercapatan 1999* Phenylcarbylamine chloride 1994* Phenyldichloroarsine 2177* Phosgene oxime 1418* Phosphorous oxychloride 177 Sarin 1584* Sec-butyl chloroformate 1175* Soman 1472* Tabun 1928* Tert-octyl mercaptan 1172* Tetraethyl dithiopyrophosphate 984* Tetraethyl lead 1392* Tetramethyl lead 1029* Tetranitromethane 1084* Trimethoxysilane 618* Trimethylacetyl chloride 743* VX 1052*

55 Software Model Data Set 8 Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2.6 ppm Breakthrough Concentration: 1 ppm Estimated Breakthrough Substance Times (minutes) Acetone cyanohydrin 12,367* Acrylonitrile 117 Allyl alcohol 1102 Allyl chlorocarbonate 3667* Bromoacetone 5874* Chloroacetone 2764* Chloroacetonitrile 1409 Chloroacetyl chloride 15,392* Chloropicrin 3914* Crotonaldehyde 2108* Cyclohexane 2198* Cyclohexyl methylphosphonate 15,433* Dibenz-(b,f)-1,4-oxazepine 16,666* Diketene 2914* Dimethyl sulfate 9355* Diphenylchloroarsine 15,253* Diphenylcyanoarsine 15,017* Diphosgene 7013* Distilled mustard 18,240* Ethyl chloroformate 2369* Ethyl chlorothioformate 6278* Ethyl phosphonothioicdichloride 12,263* Ethyl phosphorodichloridate 11,115* Ethylene dibromide 15,524* Hexachlorocyclopentadiene 16,283* Hexaethyl tetraphosphate 5852* Iso-butyl chloroformate 6073* Iso-propyl chloroformate 3773* Lewisite 15,852* Methanesulfonyl chloride 6392* Methyl orthosilicate 5029* Methyl parathion 12,748* Methyl phosphonic dichloride 7741* Mustard, lewisite mixture 16,609* Nitrogen mustard HN-1 13,788* Nitrogen mustard HN-2 13,813* Nitrogen mustard HN-3 17,176* n-propyl chloroformate 3714* o-chlorobenzylidene malononitrile 16,060* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 13,590* Parathion 12,515* Perchloromethyl mercaptan 9922* Phenyl mercapatan 13,037* Phenylcarbylamine chloride 16,196* Phenyldichloroarsine 19,886* Phosgene oxime 5901* Phosphorous oxychloride 518 Sarin 9623* Sec-butyl chloroformate 7104* Soman 11,623* Tabun 16,599* Tert-octyl mercaptan 8365* Tetraethyl dithiopyrophosphate 10,656* Tetraethyl lead 11,905* Tetramethyl lead 6217* Tetranitromethane 5884* Trimethoxysilane 2477* Trimethylacetyl chloride 3613* VX 11,028*

56

Software Model Data Set 9 Conditions: Temperature: 25ºC Relative Humidity: 25% Flow Rate: 64 LPM # of Canisters: 1 Estimated Breakthrough) Concentration Breakthrough Substance (ppm) Conc (ppm) Times (minutes) Acrylonitrile (IDLH) 85 10 93 (TLV) 2 1 351 0.2 0.1 339 0.02 0.01 212 Allyl Alcohol (IDLH) 20 10 802 (TLV) 0.5 0.1 248 0.05 0.01 0 Chloroacetyl choride No IDLH (TLV) 0.05 0.01 478,110 Chloropicrin (IDLH) 2 1 7159 (TLV) 0.1 0.01 17,065 0.01 0.001 0 Crotonaldehyde (IDLH) 50 10 519 No TLV Cyclohexane (IDLH) 1300 10 29 (TLV) 100 10 242 10 1 1077 1 0.1 3370 0.1 0.01 3627 Dimethyl sulfate (IDLH) 7 1 5544 (TLV) 0.1 0.01 60,616 0.01 0.001 77,627 Perchloromethyl mercaptan (IDLH) 10 1 3860 (TLV) 0.1 0.01 119,567 Phenyl mercapatan No IDLH (TLV) 0.1 0.01 170,082 Tetranitromethane (IDLH) 4 1 5429 (TLV) 0.005 0.001 Too low for software model

57

Software Model Data Set 10 Conditions: Temperature: 25ºC Relative Humidity: 80% Flow Rate: 64 LPM # of Canisters: 1 Estimated Breakthrough Concentration Breakthrough Substance (ppm) Conc (ppm) Times (minutes) Acrylonitrile (IDLH) 85 10 62 (TLV) 2 1 229 0.2 0.1 220 Allyl alcohol (IDLH) 20 10 690 (TLV) 0.5 0.1 175 0.05 0.01 0 Chloroacetyl chloride No IDLH (TLV) 0.05 0.01 342,826 Chloropicrin (IDLH) 2 1 4986 (TLV) 0.1 0.01 11,340 0.01 0.001 0 Crotonaldehyde (IDLH) 50 10 407 No TLV Cyclohexane (IDLH) 1300 10 25 (TLV) 100 10 183 10 1 755 1 0.1 2258 0.1 0.01 2380 Dimethyl sulfate (IDLH) 7 1 4425 (TLV) 0.1 0.01 41,089 0.01 0.001 51,059 Perchloromethyl mercaptan (IDLH) 10 1 3182 (TLV) 0.1 0.01 84,274 Phenyl mercapatan No IDLH (TLV) 0.1 0.01 122,582 Tetranitromethane (IDLH) 4 1 4061 (TLV) 0.005 0.001 Too low for software model

58 Software Model Data Set 1A Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2600 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Hexaethyl tetraphosphate 0 Methyl parathion 5 o-chlorobenzylidene malononitrile 5 Tetraethyl dithiopyrophosphate 6 Parathion 7 VX 7 Diphenylchloroarsine 8 Diphenylcyanoarsine 8 o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 8 Phosphorous oxychloride 10 Dibenz-(b,f)-1,4-oxazepine 11 Nitrogen mustard HN-3 11 Tetraethyl lead 11 Cyclohexyl methylphosphonate 12 Soman 12 Hexachlorocyclopentadiene 13 Tabun 13 Tert-octyl mercaptan 13 Methyl orthosilicate 14 Nitrogen mustard HN-1 14 Trimethoxysilane 14 Phenyldichloroarsine 15* Cyclohexane 16* Nitrogen mustard HN-2 16* Tetramethyl lead 16* Trimethylacetyl chloride 16* Acrylonitrile 17* Distilled mustard 17* Iso-butyl chloroformate 17* Phenylcarbylamine chloride 17* Sec-butyl chloroformate 17* Iso-propyl chloroformate 18* n-propyl chloroformate 18* Sarin 18* Tetranitromethane 18* Allyl chlorocarbonate 19* Diphosgene 19* Ethyl phosphorodichloridate 19* Ethyl phosphonothioicdichloride 20* Mustard, lewisite mixture 20* Chloropicrin 21* Crotonaldehyde 21* Ethyl chloroformate 21* Lewisite 21* Perchloromethyl mercaptan 21* Ethyl chlorothioformate 22* Phenyl mercapatan 23* Dimethyl sulfate 24* Acetone cyanohydrin 25* Chloroacetone 25* Ethylene dibromide 26* Methyl phosphonic dichloride 26* Allyl alcohol 27* Bromoacetone 27* Diketene 28* Phosgene oxime 28* Chloroacetyl chloride 30* Methanesulfonyl chloride 31* Chloroacetonitrile 34*

59 Software Model Data Set 2A Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 260 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Hexaethyl tetraphosphate 17 Phosphorous oxychloride 48 Acrylonitrile 58 Methyl parathion 78* Tetraethyl dithiopyrophosphate 79* VX 86* Parathion 93* o-chlorobenzylidene malononitrile 97* Trimethoxysilane 102* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 108* Diphenylcyanoarsine 110* Cyclohexane 112* Diphenylchloroarsine 114* Tetraethyl lead 131* Methyl orthosilicate 134* Tert-octyl mercaptan 135* Trimethylacetyl chloride 135* Dibenz-(b,f)-1,4-oxazepine 139* Soman 143* Nitrogen mustard HN-3 145* Cyclohexyl methylphosphonate 148* Tetramethyl lead 148* Iso-propyl chloroformate 151* Ethyl chloroformate 152* n-propyl chloroformate 152* Allyl alcohol 154* Allyl chlorocarbonate 157* Crotonaldehyde 158* Iso-butyl chloroformate 159* Sec-butyl chloroformate 160* Hexachlorocyclopentadiene 161* Nitrogen mustard HN-1 165* Chloropicrin 167* Tetranitromethane 167* Tabun 168* Diphosgene 179* Sarin 180* Nitrogen mustard HN-2 185* Chloroacetone 187* Phenyldichloroarsine 190* Ethyl chlorothioformate 193* Phenylcarbylamine chloride 193* Ethyl phosphonothioicdichloride 206* Distilled mustard 209* Diketene 210* Ethyl phosphorodichloridate 210* Chloroacetonitrile 212* Perchloromethyl mercaptan 212* Ethylene dibromide 216* Mustard, lewisite mixture 227* Phosgene oxime 235* Lewisite 236* Bromoacetone 238* Phenyl mercapatan 242* Methyl phosphonic dichloride 247* Dimethyl sulfate 261* Acetone cyanohydrin 271* Methanesulfonyl chloride 282* Chloroacetyl chloride 286*

60 Software Model Data Set 3A Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 26 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acrylonitrile 181 Phosphorous oxychloride 264 Hexaethyl tetraphosphate 468* Allyl alcohol 653* Trimethoxysilane 704* Cyclohexane 738* Crotonaldehyde 855* Ethyl chloroformate 902* Chloroacetonitrile 919* Trimethylacetyl chloride 978* Tetraethyl dithiopyrophosphate 1018* n-propyl chloroformate 1068* Iso-propyl chloroformate 1070* VX 1070* Chloroacetone 1081* Allyl chlorocarbonate 1086* Methyl orthosilicate 1104* Chloropicrin 1150* Methyl parathion 1167* Parathion 1194* Diketene 1200* Tetramethyl lead 1264* Tert-octyl mercaptan 1313* Iso-butyl chloroformate 1320* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 1343* Tetranitromethane 1343* Sec-butyl chloroformate 1400* Diphenylcyanoarsine 1420* Tetraethyl lead 1429* o-chlorobenzylidene malononitrile 1437* Diphenylchloroarsine 1453* Diphosgene 1498* Ethyl chlorothioformate 1515* Soman 1529* Ethylene dibromide 1543* Sarin 1577* Phosgene oxime 1587* Dibenz-(b,f)-1,4-oxazepine 1679* Cyclohexyl methylphosphonate 1696* Bromoacetone 1699* Nitrogen mustard HN-3 1771* Nitrogen mustard HN-1 1775* Hexachlorocyclopentadiene 1825* Perchloromethyl mercaptan 1870* Nitrogen mustard HN-2 1922* Methyl phosphonic dichloride 1926* Tabun 1937* Ethyl phosphonothioicdichloride 1956* Ethyl phosphorodichloridate 1965* Methanesulfonyl chloride 1976* Phenylcarbylamine chloride 2054* Phenyldichloroarsine 2180* Dimethyl sulfate 2185* Phenyl mercapatan 2237* Acetone cyanohydrin 2275* Distilled mustard 2285* Mustard, lewisite mixture 2325* Lewisite 2345* Chloroacetyl chloride 2566*

61 Software Model Data Set 4A Conditions: Temperature: 25ºC Relative Humidity 25% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2.6 ppm Breakthrough Concentration: 1 ppm Estimated Breakthrough Substance Times (minutes) Acrylonitrile 182 Phosphorous oxychloride 790 Allyl alcohol 1445* Chloroacetonitrile 2131* Crotonaldehyde 2935* Trimethoxysilane 3213* Cyclohexane 3232* Ethyl chloroformate 3492* Chloroacetone 3979* Diketene 4298* Trimethylacetyl chloride 5128* Allyl chlorocarbonate 5252* n-propyl chloroformate 5292* Iso-propyl chloroformate 5341* Chloropicrin 5584* Hexaethyl tetraphosphate 6256* Methyl orthosilicate 6778* Phosgene oxime 7079* Ethylene dibromide 7793* Tetranitromethane 7986* Iso-butyl chloroformate 8128* Bromoacetone 8259* Tetramethyl lead 8277* Ethyl chlorothioformate 8604* Methanesulfonyl chloride 8999* Sec-butyl chloroformate 9268* Diphosgene 9327* Sarin 10,004* Tert-octyl mercaptan 10,135* Methyl phosphonic dichloride 10,486* Tetraethyl dithiopyrophosphate 10,727* VX 11,044* Dimethyl sulfate 12,353* Parathion 12,583* Perchloromethyl mercaptan 12,716* Tetraethyl lead 12,836* Acetone cyanohydrin 12,859* Soman 12,932* Methyl parathion 13,501* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 13,604* Ethyl phosphorodichloridate 13,744* Ethyl phosphonothioicdichloride 14,667* Diphenylcyanoarsine 15,144* Nitrogen mustard HN-1 15,208* Diphenylchloroarsine 15,316* Cyclohexyl methylphosphonate 15,362* Nitrogen mustard HN-2 15,705* Phenyl mercapatan 16,112* Dibenz-(b,f)-1,4-oxazepine 16,743* o-chlorobenzylidene malononitrile 16,765* Hexachlorocyclopentadiene 16,969* Nitrogen mustard HN-3 17,377* Tabun 17,471* Phenylcarbylamine chloride 17,785* Lewisite 18,478* Mustard, lewisite mixture 18,912* Chloroacetyl chloride 19,372* Distilled mustard 19,807* Phenyldichloroarsine 20,531*

62 Software Model Data Set 5A Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2600 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Hexaethyl tetraphosphate 0 Methyl parathion 4 o-chlorobenzylidene malononitrile 5 Tetraethyl dithiopyrophosphate 5 Parathion 6 VX 6 Diphenylcyanoarsine 7 Diphenylchloroarsine 8 o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 8 Phosphorous oxychloride 8 Dibenz-(b,f)-1,4-oxazepine 10 Nitrogen mustard HN-3 10 Cyclohexyl methylphosphonate 11 Tetraethyl lead 11 Soman 12 Tabun 12 Hexachlorocyclopentadiene 13 Tert-octyl mercaptan 13 Methyl orthosilicate 14 Nitrogen mustard HN-1 14 Phenyldichloroarsine 14 Trimethoxysilane 14 Acrylonitrile 15* Cyclohexane 15* Tetramethyl lead 15* Trimethylacetyl chloride 15* Distilled mustard 16* Nitrogen mustard HN-2 16* Phenylcarbylamine chloride 16* Sec-butyl chloroformate 16* Iso-butyl chloroformate 17* Iso-propyl chloroformate 17* Allyl chlorocarbonate 18* n-propyl chloroformate 18* Sarin 18* Tetranitromethane 18* Diphosgene 19* Ethyl chloroformate 19* Ethyl phosphorodichloridate 19* Mustard, lewisite mixture 19* Chloropicrin 20* Ethyl phosphonothioicdichloride 20* Ethyl chlorothioformate 21* Lewisite 21* Perchloromethyl mercaptan 21* Crotonaldehyde 22* Phenyl mercapatan 23* Chloroacetone 24* Dimethyl sulfate 24* Acetone cyanohydrin 25* Ethylene dibromide 25* Methyl phosphonic dichloride 26* Bromoacetone 27* Diketene 27* Phosgene oxime 27* Allyl alcohol 28* Chloroacetyl chloride 29* Methanesulfonyl chloride 31* Chloroacetonitrile 32*

63 Software Model Data Set 6A Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 260 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Hexaethyl tetraphosphate 14 Phosphorous oxychloride 33 Acrylonitrile 41 Methyl parathion 64 Tetraethyl dithiopyrophosphate 73 o-chlorobenzylidene malononitrile 80* VX 82* Parathion 86* Cyclohexane 88* Trimethoxysilane 99* Diphenylcyanoarsine 100* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 104* Diphenylchloroarsine 105* Trimethylacetyl chloride 113* Methyl orthosilicate 119* Ethyl chloroformate 123* Iso-propyl chloroformate 129* n-propyl chloroformate 129* Tert-octyl mercaptan 129* Tetraethyl lead 131* Tetramethyl lead 131* Allyl chlorocarbonate 132* Crotonaldehyde 132* Dibenz-(b,f)-1,4-oxazepine 135* Chloropicrin 141* Nitrogen mustard HN-3 141* Soman 143* Iso-butyl chloroformate 145* Sec-butyl chloroformate 147* Cyclohexyl methylphosphonate 148* Allyl alcohol 150* Tetranitromethane 150* Chloroacetone 157* Hexachlorocyclopentadiene 160* Diphosgene 163* Nitrogen mustard HN-1 165* Tabun 166* Chloroacetonitrile 169* Ethyl chlorothioformate 173* Diketene 175* Sarin 181* Nitrogen mustard HN-2 185* Ethylene dibromide 187* Phenyldichloroarsine 188* Phenylcarbylamine chloride 193* Perchloromethyl mercaptan 200* Ethyl phosphonothioicdichloride 201* Ethyl phosphorodichloridate 206* Distilled mustard 209* Bromoacetone 212* Phosgene oxime 224* Mustard, lewisite mixture 226* Methyl phosphonic dichloride 230* Lewisite 234* Phenyl mercapatan 235* Dimethyl sulfate 253* Methanesulfonyl chloride 258* Chloroacetyl chloride 264* Acetone cyanohydrin 271*

64 Software Model Data Set 7A Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 26 ppm Breakthrough Concentration: 10 ppm Estimated Breakthrough Substance Times (minutes) Acrylonitrile 119 Phosphorous oxychloride 177 Hexaethyl tetraphosphate 396* Cyclohexane 531* Allyl alcohol 571* Trimethoxysilane 618* Chloroacetonitrile 643* Crotonaldehyde 655* Ethyl chloroformate 655* Trimethylacetyl chloride 743* Chloroacetone 809* n-propyl chloroformate 812* Allyl chlorocarbonate 820* Iso-propyl chloroformate 820* Chloropicrin 870* Diketene 878* Methyl orthosilicate 895* Tetraethyl dithiopyrophosphate 984* Tetramethyl lead 1029* VX 1052* Iso-butyl chloroformate 1083* Methyl parathion 1083* Tetranitromethane 1084* Parathion 1156* Tert-octyl mercaptan 1172* Sec-butyl chloroformate 1175* Ethylene dibromide 1192* Ethyl chlorothioformate 1213* Diphosgene 1238* o-chlorobenzylidene malononitrile 1290* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 1332* Bromoacetone 1335* Diphenylcyanoarsine 1364* Tetraethyl lead 1392* Diphenylchloroarsine 1409* Phosgene oxime 1418* Soman 1472* Methanesulfonyl chloride 1570* Sarin 1584* Methyl phosphonic dichloride 1587* Perchloromethyl mercaptan 1607* Dibenz-(b,f)-1,4-oxazepine 1674* Cyclohexyl methylphosphonate 1696* Nitrogen mustard HN-1 1722* Ethyl phosphorodichloridate 1769* Nitrogen mustard HN-3 1769* Ethyl phosphonothioicdichloride 1779* Hexachlorocyclopentadiene 1816* Nitrogen mustard HN-2 1834* Dimethyl sulfate 1885* Tabun 1928* Phenylcarbylamine chloride 1994* Phenyl mercapatan 1999* Phenyldichloroarsine 2177* Chloroacetyl chloride 2197* Lewisite 2200* Mustard, lewisite mixture 2220* Distilled mustard 2247* Acetone cyanohydrin 2288*

65 Software Model Data Set 8A Conditions: Temperature: 25ºC Relative Humidity 80% Flow Rate: 64 LPM # of Canisters: 1 Contaminant Concentration: 2.6 ppm Breakthrough Concentration: 1 ppm Estimated Breakthrough Substance Times (minutes) Acrylonitrile 117 Phosphorous oxychloride 518 Allyl alcohol 1102 Chloroacetonitrile 1409 Crotonaldehyde 2108* Cyclohexane 2198* Ethyl chloroformate 2369* Trimethoxysilane 2477* Chloroacetone 2764* Diketene 2914* Trimethylacetyl chloride 3613* Allyl chlorocarbonate 3667* n-propyl chloroformate 3714* Iso-propyl chloroformate 3773* Chloropicrin 3914* Methyl orthosilicate 5029* Hexaethyl tetraphosphate 5852* Bromoacetone 5874* Tetranitromethane 5884* Phosgene oxime 5901* Iso-butyl chloroformate 6073* Tetramethyl lead 6217* Ethyl chlorothioformate 6278* Methanesulfonyl chloride 6392* Diphosgene 7013* Sec-butyl chloroformate 7104* Methyl phosphonic dichloride 7741* Tert-octyl mercaptan 8365* Dimethyl sulfate 9355* Sarin 9623* Perchloromethyl mercaptan 9922* Tetraethyl dithiopyrophosphate 10,656* VX 11,028* Ethyl phosphorodichloridate 11,115* Soman 11,623* Tetraethyl lead 11,905* Ethyl phosphonothioicdichloride 12,263* Acetone cyanohydrin 12,367* Parathion 12,515* Methyl parathion 12,748* Phenyl mercapatan 13,037* o-ethyl-s-(2isopropyaminoethyl)-methyl phosphothiolate 13,590* Nitrogen mustard HN-1 13,788* Nitrogen mustard HN-2 13,813* Diphenylcyanoarsine 15,017* Diphenylchloroarsine 15,253* Chloroacetyl chloride 15,392* Cyclohexyl methylphosphonate 15,433* Ethylene dibromide 15,524* Lewisite 15,852* o-chlorobenzylidene malononitrile 16,060* Phenylcarbylamine chloride 16,196* Hexachlorocyclopentadiene 16,283* Tabun 16,599* Mustard, lewisite mixture 16,609* Dibenz-(b,f)-1,4-oxazepine 16,666* Nitrogen mustard HN-3 17,176* Distilled mustard 18,240* Phenyldichloroarsine 19,886*

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