Phone: Lindsay Hill, CIH: (205) 640- 7305 (Direct); (205) 937-3321 (Cell)
William Garvin, CI H: (205) 419-5124 (Direct); (205) 903-5106 (Cell) E-mail: info@directcih.com 70 Cherokee Lane Pell City, Alabama 35128 http://directcih.com 

## D IRECT 

## CIH

INDUSTRIAL HYGIENE MONI TORING INVESTIGATION

& 

### OCCUPATIONAL EXPOSU RE ASSESSMENT

OF 

### 2-BROMO 3,3,3-TRIFLUOROPROPENE

FOR



### AMERICAN PACIFIC CORPORATION, HALOTRON DIVISION CEDAR CITY, UTAH

Prepared for Bradford Colton , Research Engineer 3883 Howard Hughes Pkwy, Suite 700 Las Vegas, Nevada 89169

By Lindsay R. Hill, CIH

Direct CIH , LLC

November 27, 20130 

## D IRECT 

## CIH

Table of Contents

1.0 SITUAT ION ............................................................................................................... 1

2.0 GO ALS .................................................................................................................... 2

3.0 METH ODS ................................................................................................................ 2

3.1 Preliminar y Information ..................................................................................... 2 3.2 Exposure Activities ............................................................................................ 5

3.3 Simulation Monitoring ........................................................................................ 8 3.3.1 Spill From Disconnection of Li quid Fill Fitting Procedure Simulation .............. 9 3.3.2 Sample Bottle Fill ing Procedure Simulation ................................................. 10

4.0 RESU LTS ............................................................................................................... 10

5. RECOMMENDAT IONS ............................................................................................. 16

6. QUALIFYING STATEMEN T ..................................................................................... 17

7. CLOS ING .................................................................................................................. 1 8

APPENDICES

APPENDIX A – SAMPLING INFORMATION, CALIBRATION DATA

APPENDIX B – AIR MONITORING INVESTIGA TION WITH R123 IN BLDG 24C AT

THE AMPAC CEDAR CITY, UTAH FACILITY

APPENDIX C—AIR MONITORING INVESTIGA TIONS WITH R123 AT THE AMEREX

TRUSSVILLE, ALABAMA FACILITY1 

## D IRECT 

## CIH

November 17, 2013

Bradford Colton, Re search Engineer American Pacific Corporation

Halotron Division 3883 Howard Hughes Pkwy

Suite 700 Las Vegas, NV 89169

1.0 SITUATION

American Pacific Corporation (AMPAC) has developed a new halogenated hydrocarbon compound to be used as a clean agent fire suppr essant alternative to Halon 1211. The new product being researched is known as Halotron BrX, or BTP , and has the chemical name 2-Bromo-3,3,3-tr ifluoro-1-propene, and CAS number 1514-82-5. This product is similar in physical properties to AMPAC’s ex isting Halotron I, or HCFC Blend B, clean agent that is an alternative to Halon 1211 and has been sold in UL listed extinguishers since 1996. The primary ingredient of Halotron I is R-123 , or HCFC-123, and comprises greater than 95% wt. of the co mposition. Due to similariti es in application and physical properties of Halotron I and BTP, it was anticipated that Halotron I would be a good surrogate for BTP. Separate monitoring studies of R-123 and BTP were completed during typical handling operat ions and a comparison of R-123 and BTP was made in

order to determine whether a correction fact or might be applied to the R-123 data to estimate what the handling exposures would be for BTP.

This industrial hygiene investigation was don e in order to (1) estimate the level of operator exposure to R-123 duri ng tasks where it is poured or spilled, (2) estimate the level of operator exposure to BTP in the same work setting, (3) determine if the R-123 monitoring data is predictive of BTP levels, and (4) use this testing as part of the process fulfilling the require ments under the Toxic Substanc es Control Act (TSCA).

Air monitoring investigations for this and prev ious related investigations, presented in the Appendices, were done over a range of work settings, ti me periods, locations, and employees for the R-123. Study locations included the AMPAC facility in Cedar City, Utah, where 1⁄2 ton steel Halotron cylinders ar e sampled and filled, and their contents tested, and at the Amerex facility in Trussville, Alabama where several portable extinguisher sizes are filled. Samplin g and analysis was done on-site with a portable dispersive infrared spectrophotometer that was placed or held in the immediate work area, or, where possible, near the breathing zone of the operator during normal work.2 

## D IRECT 

## CIH

This report describes the air monitoring and results of the R-123 and BTP during the

execution of different tasks at the Cedar Cit y AMPAC facility. An effort is made to generate a correction factor to apply to the R-123 averages to predict BTP

concentrations that would be found under sim ilar conditions, and to see if tentative occupational exposure levels (OELs) for BTP are met.

2.0 GOALS

Monitoring events took place between March and October of 2013. They were done both to assess worker exposure to R-123 during various work practices and periods, and as part of a larger effort, to co mpare the behavior and consequent airborne concentrations of R-123 with BTP in exposure si mulations. Since there are similarities in the physical properties of the two compounds, it was hoped that by duplicating work practices as closely as possible during moni toring events with first one compound, then the other, it might be possible to assume t he same exposures for the same types of operations. If there were differences, perhaps a compensation or adjustment value

could be determined. This could then be applied to the R-123 monitoring levels previously and more easily determined in order to estimate BTP levels in the same situation. The primary goal is that idea lly, a valid, though tentative OEL for BTP will emerge from this work.

3.0 METHODS

3.1 Preliminary Information

Lindsay Hill, a certified industr ial hygienist (CIH) with Direct CIH , visited the AMPAC Cedar City, Utah Halotron facility during the week of October 28 th , 2013. Over three days Mr. Hill logged over 10 hours of air monitoring during R-123 and BTP handling in Building 24C. The R-123 liquid is regular ly transferred via high pressure lines with quick-connect fittings from a ~75,000 lb. capacity insulated pe rmanent tank in the back room of the building (it is filled once or twice a mont h from a tank truck) to 1⁄2 ton steel cylinders (1000 lb. water capacit y, with capacity of up to 1,200 lbs of Halotron I) designated by DOT as 4B W260 vessels. Occasionally 500 lb and smaller cylinders are also filled. Used cylinders are routinely sampled and rinsed internally with R-123, and the contents anal yzed, before refilling for shipment to various fire extinguisher companies for co mmercial and retail distribution. The R123 is mixed with smaller amounts of CF 4 and Argon, less than 7% wt, in the cylinders for optimal pressure, fill level, and application performance characteristics.3 

## D IRECT 

## CIH

The analyzer used for air monitoring was a Thermo Scientific Miran Sapphire Ambient Air Analyzer, Model 205A, Serial Number S00089. The instrument uses single beam dispersive infrared (IR) spectr ophotometry in a port able unit with factory calibration of the gases under study. Sa mple air enters an ex tendable probe at 14 liters per minute. A micropr ocessor automatically controls the analysis, processes the measurement signal, and calculates the absorbance values. Internal adjustments were made for humidity, elev ation, and reference compensation (to reduce electronic drift) using algorithms. The instrument is zeroed using activated charcoal cartridges prior to each use. The compound’s absorbance wavelength and the IR beam path length used for each log ar e manually selected to minimize cross sensitivities and maximize sensitivity to t he compound of interest, respectively. The electrical supply is generally provided by an internal battery, but because of the sample duration and a limited nee d for mobility this applic ation used 110 volts AC

from a wall outlet.

Thermo Scientific states t hat the analytical accuracy for R-123 is within 10% of the reading with a detection limit of 0.07 ppm. For BTP the instru ment reading was

within 1.5% of the calibra tion value with a detection lim it of 0.17 ppm. Factory inspection, calibration and maintenance of the instrument were performed immediately prior to this in vestigation by Thermo Scient ific. The documentation of

this information is detailed in Appendix A following this report.

The instrument analyzes twice per sec ond, and the data are averaged every ten seconds. In the configuration used her e, one data point (in this case compound concentration in parts per million, pp m) was stored in the analyzer every 30 seconds. This information was then downloaded and is presented in tabulated summaries below, and also in annotated graphs of concentration over time. All of the logged data from earlier investigations of the R-123 is presented in graphs in Appendices B and C follo wing this report.

Building 24C consists of a small front o ffice, the main room where this monitoring event was conducted, and a back room wher e the large R-123 tank is housed. The main room is approximately 70, 000 cubic feet in volume. There is a large bay door and office doors in the front (closed during monitoring, but which may or may not be open during operations), and a door to the back room (open during monitoring, as is normal during operations). Back room doors to the outside were closed during monitoring, as is normal. The operator does his work with the cylinders positioned on

a floor scale next to a work table that is towards the back of t he main room. Figure 1, on the following page, shows a 1⁄2 ton cylinder on the scale, work table, and analyzer.4 

## D IRECT 

## CIH

Figure 1: Layout of work area in Building 24C showing IR analyzer, 1⁄2 ton cylinder, and work table with quick connect fittings.

There are no windows, but a 32 inch di ameter propeller style fan operates continuously moving air from the main r oom into the back r oom to provide air movement for the operator, and to keep te mperatures above freezing in the back room. The fan is approximat ely 14 feet from t he operator’s primar y activities when working with R-123 or BTP. Measurements were made at 21 locations within the fan opening with an impeller anemometer to dete rmine average flow. Average air flow

was calculated that 5736 cubic feet of ai r are moved per minute, and that 4.9 air changes per hour take place in the main room.5 

## D IRECT 

## CIH

Two large ceiling mounted t hermostatically controlled hea ters with blower fans are

on one side of the main room. One is about 12 feet from the wo rk table where the operator stands to conduct filling activities for the cylinder on the scale, or will sit behind to complete paperwork. The heaters are tilted down, and the heater closest

to the work area and table is oriented towa rds the back of the ma in room so that

there is a directed current of air from the heater past the oper ator, and out through

the fan to the back room wh ile in operation. Due to cold weather during the monitoring event the heater fan would intermi ttently turn on and off. The warm air movement increased dispersal and evaporation of product.

3.2 Exposure Activities

The operations at the Cedar City, Utah AMPAC Halotron facility are typically performed by a single operator. Air monitoring focused on the operator’s work area and specifically, the operator breathing zone during activities involving material handling and cylinder preparatio n. The operator may also complete a portion of the day in the front office, which was s hown to be clear of any halogenated agent concentrations. The operator’s protective equipment includes steel toed boots, eye protection, and thick nitrile gloves when handling product or product equipment. After discussions between Halotron engine ering, plant personnel, and AMPAC’s toxicologist consultant working with the BTP, it was determined that five functions occur in Building 24C duri ng the handling of product:

(1) Preparing new containers – transferring agent in and rinsing (rinsed agent transferred in closed system to waste tank) – closed system,

(2) Transferring base (a mixture of R-123 and Ar) – transferring base through hoses into bulk tank – closed system,

(3) Transferring gases (CF 4 or Ar) - transferring gas through hoses into bulk tank – closed system,

(4) Sampling – transfer of liqui d into bottles - open system, and

(5) Venting – returned containers need argon pressure vented to be refilled – this used to be done with a vacuum hood placed above the valve, but now uses a direct

hose connection that vent s the tank outside the building– closed system.

It was originally assumed that sinc e (4) sampling was the only open system operation among these activities, it would be the only one with potential exposure.6 

## D IRECT 

## CIH

After observing the operator conduct the va rious operations, it was quickly realized that even though quick-connect fittings were fast and convenient, product was lost due to adaptors used to fit the quick connec t to the cylinder valves. The 1⁄2 ton cylinders used to store final product have a vapor and liquid valve with a CGA 660 fitting. Quick-connect fittings are attached to these valves using CGA and pipe fittings. When liquid transfer operations were complete, the removal of the fill fitting connected to the liquid valve would squirt small amounts of product when disconnected, or spill product when tilted af ter disconnecting. Once disconnected, the fill fitting is returned to its storage loca tion on the side of the work table. The product, whatever was being transferred, would spill onto the top shoulder of the 1⁄2 ton cylinder and run down, or splash dire ctly onto the concrete floor. As the

shoulder of the bottle is close to breat hing zone height and t he product evaporates extremely fast (refe r to Table 5), the opportunity for inhalation was frequent.

During the monitoring, it was determined that a ball valve and quick connect on the liquid transfer line were worn out causing additional airborne c oncentrations. The operator indicated that it was difficult to determine a timely maintenance schedule for these, which were replaced prior to the ai r monitoring events. Note fittings in the bottom corner of Figure 2.7 

## D IRECT 

## CIH

Figure 2: Operator simulati ng spill from quick connect fitting onto shoulder of 1⁄2 ton cylinder. Note relation of heater, breathi ng zone of operator, spill location, and monitor probe (bottom). Air flow is from th e heater towards the monitor probe.8 

## D IRECT 

## CIH

3.3 Simulation Monitoring

There were several choices in selecting an exposure scenario to monitor. The two scenarios which result in the highest exposur es were selected. The first scenario was designed to simulate the sample bottl e filling operation, as this is an open system, an obvious source of some expos ure, and because it is done frequently. The second exposure scenario involved simu lating a spill from the disconnection of the liquid fill fitting, which resulted in a rel ease of material onto the cylinder shoulder. The operator estimated the volume of pr oduct typically lost when disconnecting the fill fitting. During the monitoring for eac h scenario, the duration of peak exposure

was a matter of a few seconds.

Figure 3: 30 ml sample and squeeze bottles.

Several issues arose during monitoring. It was determined that there was some cross sensitivity between the two compounds, so that w hen the analyzer was set to the absorbance wavelength of R- 123, it would also respond to a lesser degree to the

BTP.

A second and larger problem was t hat the R-123 left an airborne residual background level after using it. The more it was used, the higher the background

level became. Product tr ansfer on Monday, October 28 th , left standing liquid within the liquid fill fittings stored at the work table. Evaporatio n caused the background level to go from 0.18 ppm initially to about 8 ppm in the main room on Tuesday,

October 29 th . The average concentrations from the analysis of R-123 could then not be used in establishing a correction factor fo r BTP, but was very useful in identifying9 

## D IRECT 

## CIH

sources of exposure. A similar background level was seen in air monitoring at the Trussville, Alabama facility, but the sour ce(s) were not as well understood because other halogenated fire extin guishing agents handled were in the vicinity of the

Halotron I fill line. Airborne concentr ations of R-123 had diminished to premonitoring levels by the next morning, and all of the logged data from October 30 th
was useful because background levels remained low.

The heater fan also caused airborne levels of product to fluctuate during monitoring,

and it could not be determined when the thermost atic control would turn the unit on, so monitoring on October 30 th was done with the heat shut off.

Each of the two simulations was comp leted twice, once using the R-123 and again using the BTP. Each simulation event, i.e., sample pour or spill, was repeated four or five times with the analyzer probe posit ioned on the edge of t he work table down draft from the operator’s face. The di stance was about four feet laterally and eighteen inches below his breathing zone. The product being poured or spilled was only one or two feet from his face (and also just below), but not in an up or down

draft direction.

A final pour/spill was completed in each simu lation event with the probe within a foot of the operator’s face to see how the com pound concentration differed from the work table position of the probe. The graphs below illustrate the concentration over time during the simulations and annotate the acti vity. Figure 2 above shows the spill

simulation.

3.3.1 Spill From Disconnection of Liqui d Fill Fitting Procedure Simulation
Spillage from the disconnection of the liquid fill fitting was the second exposure

scenario evaluated. In order to transfer liquid product into the 1⁄2 ton cylinders, a liquid fill fitting with a male Parker qui ck-connect is attached to the CGA 660 fitting on the cylinder. A transfer hose lead ing from the 75,000 lb. bulk tank is equipped with a female quick-connect. The male quick-connect that is attached to the cylinder is removed once liquid transfer operations are complete. Disconnection of this fitting results in a small amount of product spillage onto the shoulder of the cylinder.

When monitoring the R-123 spills, the cyli nder fitting was tilted onto the shoulder of the cylinder during disconnection. The fitting was then set, vertically, in its storage location on the side of the work table. The simulation with R-123 and BTP was completed by filling 30 ml bottl es with the estimat ed amount of liquid that spilled from the fitting, about 4 ml. At 5-minute intervals, the 4 ml of product (contained in each 30 ml bottle) was poured onto the shoulder of the 1⁄2 ton cylinder. Figure 2 above shows the spill simulation.10 

## D IRECT 

## CIH

These measurements were completed on October 30 th and the heater was

turned off.

3.3.2 Sample Bottle Fill ing Procedure Simulation
Sampling of final product is completed by attaching the sampling port onto the liquid valve of the 1⁄2 ton cylinder, transfe rring liquid into a 500 ml Nalgene bottle, and then into a 30 ml glass bottle. These two bottles are then sent to the lab for quality analysis. When simulating this event, which was performed with both R123 and BTP, the filling of a sample bottl e was limited to a single bottle using a squeeze bottle to mimic the transfer of li quid from a sampling port. Since the intent of this simulation was to determine a comparison between R-123 and BTP, it was desirable to closely mimic a standar d procedure. The diameter of the squeeze bottle orifice was increased until the flow rate was about the same as the flow rate coming from the sample port. Figure 3 shows the 30 ml sample and squeeze bottles used for the simulation of sample bottle filling.

This testing was completed on October 29 th . The heater fan operated intermittently.

4.0 RESULTS

The following four graphs and accompanying tables present the logged data from each of the four approximat ely 30 minute simulation events discussed above. Figure 4 and Table 1 correspond to the R-123 sampling bottle filling. Figure 5 and Table 2 correspond to the BTP sample bottle filli ng simulation. Figures 6 and 7 and their corresponding Tables, 3 and 4, likewise, repr esent results from the R-123 spills and BTP simulation spills. The oper ator breathing zone peaks in t he last three monitor logs were not included in the calculated average ex posure level to reduce variability (note that in Table 1, the operator breathing zone concentration was similar to the other four peaks thereby not increasing vari ability, and allowed for five peaks in calculation of an average concentration). Oper ator actions, heater operation, and other factors influence the variability between peaks within each simulation.11 

## D IRECT 

## CIH

Figure 4: R-123 sample bottle filling. No te residual background level of about 8 ppm.

Table 1. R-123 Sample Bottle Filling Data from 33 Minute Log

Peak 1 Peak 2 Peak 3 Peak 4 Peak 5

Max level 67.6 ppm Max level 47.3 ppm Max level 31.5 ppm Max level 31.3 ppm Max level 29.9 ppm Above 10 ppm

120 seconds Above 10 ppm

90 seconds Above 10 ppm

120 seconds Above 10 ppm

120 seconds Above 10 ppm

90 seconds 6% of log time 4.5% of log

time 6% of log time 6% of log time 4.5% of log

time 179% of peak

average 125% of peak

average 83% of peak

average 83% of peak

average 79% of peak

average12 

## D IRECT 

## CIH

Figure 5: BTP sample bottle filling simulation.

Table 2. BTP Sample Bottle Filling Data with Probe at Table 33 Minute Log

Peak 1 Peak 2 Peak 3 Peak 4 Peak 5

Max level 21.2 ppm Max level 24.6 ppm Max level 17.0 ppm Max level 27.8 ppm Max level 20.0 ppm Above 10 ppm

30 seconds Above 10 ppm

60 seconds Above 10 ppm

60 seconds Above 10 ppm

30 seconds Above 10 ppm

30 seconds 1.5% of log

time 3% of log time 3% of log time 1.5% of log

time 1.5% of log

time 96% of peak

average 113% of peak

average 77% of peak

average 126% of peak

average 90% of peak

average13 

## D IRECT 

## CIH

Figure 6: R-123 spills fr om the quick disconnect fitting

Table 3. R-123 Fitting Spills Data with Probe at Table from 32 Minute Log

Peak 1 Peak 2 Peak 3 Peak 4 Peak 5

Max level 11.5 ppm Max level 42.3 ppm Max level 32.1 ppm Max level 32.9 ppm Max level 20.2 ppm Above 10 ppm

60 seconds Above 10 ppm

60 seconds Above 10 ppm

60 seconds Above 10 ppm

60 seconds Above 10 ppm

60 seconds 3% of log time 3% of log time 3% of log time 3% of log time 3% of log time

41% of peak

average 152% of peak

average 115% of peak

average 118% of peak

average 73% of peak

average14 

## D IRECT 

## CIH

Figure 7: BTP spill simu lation from 30 ml bottles onto cylinder shoulder. Note: 4.2 ppm average based on min + ma x values; 5.0 ppm value used below

Table 4. BTP Fitting Spills Si mulation Data with Probe at Table 34 Minute Log

Peak 1 Peak 2 Peak 3 Peak 4 Peak 5

Max level 14.8 ppm Max level 45.4 ppm Max level 62.6 ppm Max level 21.4 ppm Max level 14.5 ppm Above 10 ppm

30 seconds Above 10 ppm

60 seconds Above 10 ppm

60 seconds Above 10 ppm

30 seconds Above 10 ppm

60 seconds 1.5% of log

time 3% of log time 3% of log time 1.5% of log

time 3% of log time

47% of peak

average 143% of peak

average 197% of peak

average 68% of peak

average 46% of peak

average15 

## D IRECT 

## CIH

A summary of the tabulated statistics from the graphed and tabulated data above indicates differences in the exposures from activities and compounds and are shown

below:

Table 5. Summary of Data fr om 30 Minute Simulation Logs

Simulation

Event Peak Levels,

ppm % of Log

as Peak ( >10 ppm) Average Levels,

ppm Standard

Deviation Vapor

Pressure

@20°C, mm Hg Vapor Density @20°C

(g/L) max avg

R-123 Sampling 67.6 37.8 27% 15.1* 13.3 580 5.14

BTP Sampling 27.8 23.4 11.5% 7.9 16.1 510 7.27

R-123 Spills 42.3 27.8 18% 11.1 10.6

BTP Spills 62.6 31.7 13% 5.0 9.7

*without background removal – subtract ing 4 ppm is commensurate with BTP Sampling log background Note: Peak level calculations do not include breathing zone peak

The averaged concentrations and standard dev iation of values reveal differences between the scenarios. Higher averages duri ng sampling, as opposed to spills, are a result of a high background leve l for the R-123, and longer periods of exposed product in the air. As the multiple peaks of va rying concentrations during the performance of tasks will attest, these graphs do not lend them selves to interpretation in terms of central tendency, but the st andard deviation values are significantly higher for the sampling events. There is greater variation in exposure levels during sampling. It is also likely that many different activities wi ll exhibit this variation in exposure levels.

The percent of the log as a peak and the av eraged log concentrations reveal differences between the compounds. The greater vapor pr essure of R-123 results in longer and16 

## D IRECT 

## CIH

higher concentration breathing zone exposures . The greater vapor density of BTP results in its rapid removal to low areas, with less inhalation time and concentration.

With background adjustment, the average R-123 levels are 141% higher than the BTP levels during the sampling scenario. T he average R-123 levels are 222% higher than the BTP levels during the spill events. As a first estimate , if the average level of R-123 that is used is 222% higher than BTP, then a multiplier of 0.45 applied to an R-123 level would make BTP levels equivalent.

Appendix B contains personnel exposure m onitoring of R-123 levels during actual operations at the Halotron production facility in Cedar City, Utah, for production of the Halotron I fire extinguishing agent. Depending on the operations taking place, the average exposure levels were between 5.3 and 13.8 ppm of R-123 for a 10 hour shift. Assuming similar handling of BT P, using the 0.45 multiplier would result in average levels between 2.4 and 6.2 ppm for a 10 hour shift.

Appendix C contains personnel exposure monitoring of R-123 during actual operations of filling UL listed portable extinguishers wit h the Halotron I fire extinguishing agent at the Amerex facility in Trussville, Alabama. The average exposure level was 2.2 ppm of R-123 for a 10 hour shift. The procedure to transfer extinguishing agent into a fire extinguisher and pressurize it with argon or nitrogen to its operating pressure would be

the same for Halotron I and BTP. Therefor e, while exposure controls could vary, operations would be similar for these products. Using the 0.45 multiplier would result in an average exposure level for BTP of 1.1 ppm for a 10 hour shift.

5. RECOMMENDATIONS

Direct CIH presents the following recommendations:

1. This monitoring reveals much of the nature of exposure between these compounds. While a correction factor is proposed here, the amount of variation

in the values from the simulations does not lend itself to a particularly valid correction or predictive fact or that can be used for the BTP. Standard deviations do not approach 100% of the averages, so the correction fact or should remain

below 1.0. More data from simulations are needed.

2. By taking advantage of the vapor density of BTP, engineering controls such as low-lying point source ventilation should be very effective in mitigating exposure.17 

## D IRECT 

## CIH

3. Rigorous adherence to a conservati ve maintenance schedule for the product transfer equipment, i.e. quick connect fitti ngs, will reduce exposure substantially.

4. Ceiling level OELs will be exceeded by concentration spikes that occurred during monitoring, and must be considered.

5. The proper placement of the operator in relation to the source of product and the

heater fan or other source s of air movement while doing his work will reduce

exposure.

6. Expanding on #5 above, any changes that physically lower the product sources

further from and below the operator’s breathing zone will reduce exposure levels.

6. QUALIFYING STATEMENT

Direct CIH presents the findings, conclusions and recommendations, herein, which are

based solely on the conditions observed dur ing the date the sampling program was

conducted. Additionally, Direct CIH does not make any representation or projection as

to past conditions or future exposures and does not extend its findings to areas outside

of the statistical repr esentation of the comple ted investigation.

The findings and conclusions of this report ar e not scientific certainties, but rather,

probabilities based on professional judgment concerning the si gnificance of the data

gathered during the course of the investigation.

Sampling and analytical results are limited in that they represent concentrations at the

time of sample collection only. Chang es in operating procedures, ventilation,

temperature, occupancy, procedures, equipm ent, sources, products used, and other

conditions may cause variations in anticipated airborne concentrations.

This report has been prepared for the exclusive use of the client. This report and its

analytical results, findings, conclusions, and recommendations, either in part or its

entirety is not to be used by any other party without prior consent of Direct CIH or the

client. Any use thereof, other than the sole benefit of Direct CIH or the client, shall be

deemed wrongful and may cause i rreparable injury to Direct CIH or the client.18 

## D IRECT 

## CIH

7. CLOSING

Direct CIH appreciates the opportunity to assist with your health and safety needs.

Please contact us if there are any questions or comments regarding this investigation.

Sincerely,

Lindsay R. Hill, CIH

Principal, Direct CIH19 

## D IRECT 

## CIH

APPENDIX A SAMPLING INFORMATION, CALIBRATION DATA20 

## D IRECT 

## CIH21 

## D IRECT 

## CIH22 

## D IRECT 

## CIH23 

## D IRECT 

## CIH

APPENDIX B

AIR MONITORING INVESTIGATION WITH R123 IN BLDG 24C AT THE AMPAC CEDAR CITY, UTAH FACILITY24 

## D IRECT 

## CIH

November 17, 2013

Bradford Colton, Re search Engineer American Pacific Corporation

Halotron Division 3883 Howard Hughes Pkwy

Suite 700 Las Vegas, NV 89169

Re: Determination of R-123 Levels in Building 24C, Cedar City, Utah Facility

On October 28 th and 29 th , 2013, Lindsay Hill, an indus trial hygienist with Direct CIH

, visited American Pacific Corpor ation’s (AMPAC) Halotron fac ility in Cedar City, Utah. The visit was made to monitor the operator ’s exposure to R-123, also known as Halotron I during product transfer operations. The chemical name is 2,2-dichloro-1,1,1-

trifluorothane.

The R-123 is a fire suppressant raw materi al that is transferred as a liquid under pressure into 1⁄2 ton cylinders, which are then shipped to fire extinguisher manufacturers. The Halotron operator conduc ts cylinder preparation, sampling, and filling of cylinders with the Halo tron I, or HCFC Blend B. The primary ingredient of

Halotron I is R-123 , or HCFC-123, and comprises greater than 95 %wt. of the composition. The remaining portions of the composition ar e comprised of CF 4 and argon (Ar). A day of operations may consist of entirely filling of final product cylinders or preparation of return cylinders.

The probe from the analyzer was held near the operator’s breathing z one, or set at the edge of his work table. It was generally withi n three or four feet of operator’s face during his work.

A Thermo MIRAN SapphIRe model 205A dis persive infrared spectrophotometer (IR)

was used to determine the levels of the R- 123. The analyzer was factory calibrated with R-123, and could be monitored individually or with other compounds in the on-board library. Annual calibration document ation is in Appendix A.

The analyzer performs two analyses per sec ond. After startup it was zeroed and warmed up for about 1⁄2 hour prior to logging. The logging configuration generated an averaged data point, or concentration in par ts per million (ppm) every 30 seconds. Levels were logged over two periods on co nsecutive days, each lasting about four hours. The data were graphed as concentrati on over time, with annotations giving average and maximum values and changes in ac tivity when they took place. The graphs are presented below. There were numer ous high concentration spikes over the25 

## D IRECT 

## CIH

logging periods.

The first graph, Figure 1, taken on the morning and early afternoon of October 28 th , was from air monitoring conducted while the operator sampled and filled seven cylinders with base, which is a mixt ure of R-123, argon, and CF 4 . In order to transfer liquid product into the 1⁄2 ton cylinders, a liquid fill fitting with a male Parker quick-connect is attached to the CGA 660 fitting on the cylinder. A transfer hose leading from the 75,000 lb permanent bulk tank is equipped with a fe male quick-connect. However, the male quick-connect that is attached to the cylinde r is removed once liquid transfer operations are complete. Disconnection of this fitting re sults in a small amount of product spillage onto the shoulder of the cylinder. The tr ansfer hose leaked at the ball valve between the filling of cylinders 2 and 3, causing a 268 ppm concentration spike of R-123. The valve was replaced and the average concentra tion over the logging period without that spike was 5.3 ppm.

The second graph, Figure 2, taken early t he next morning, was logged during and after the preparation of return cylinders. In order to reuse empty cylinder s that are returned from customers, a small am ount of base is added to the cylinders through the cylinder vapor valve. This rinses the interior of the cylinder and provides a level of liquid product that may be removed to check for physical contaminants and moisture contamination.

Product from the cylinder was transferred to open sample bottles and a small amount of spillage from the sample port took place. Af ter this, the liquid fill fitting attached to the vapor valve was removed, which also resulted in about 4 ml of spillage. These spillages all contributed to frequent concentration spikes and a buildup of a high (10-15 ppm) background concentration, which only slowly subsided. The average

concentration over the log was 13.8 ppm.

Note that high concentrations of R-123 are ex hibited during early work (October 28 and 29, 2013) These higher concentrations of R-123 occurred because the operator was attempting to create a worst case scenario, and residual levels were amplified due to liquid product remaining in fittings (this situation was rectified).26 

## D IRECT 

## CIH

Figure 1: R-123 levels logged in Building 24C on October 28, 201327 

## D IRECT 

## CIH

Figure 2: R-123 levels logged in Building 24C on October 29, 2013

Please feel free to contact Direct CIH if you have any questions regarding this work.

Sincerely,

Lindsay R. Hill, CIH Principal, Direct CIH LLC28 

## D IRECT 

## CIH

APPENDIX C

AIR MONITORING INVESTIGATIONS WITH R123 AT THE AMEREX TRUSSVILLE, ALABAMA FACILITY29 

## D IRECT 

## CIH

March 25, 2013

Will Yarbrough, Safety Director Fred Goodnight, VP Engineering

Amerex Corporation 7595 Gadsden Highway

Post Office Box 81 Trussville, Alabama 35173-0081

Re: Determination of Halotron I Lev els at the Fill Station, Dept. 04

On March 13, 2013, Lindsay Hill, an industrial hygienist with Direct CIH , visited the Amerex facility in Trussville, Alabama. Consideration of a new formulation of halon extinguisher lead to a need to quantify, to the best extent po ssible, the exposure levels among personnel filling the extinguishers at the facility. There are several uncertainties in establishing time-weighted average exposures the employees receive. They include working ten hour shifts, the changing of bottl e sizes and extinguisher volumes during a shift, occasional spikes in the halon concentra tion, attributes particular to the operator, and operator movement in the area. T he new halon formulation being considered (Halotron II), while brominated rather t han chlorinated, has physical and chemical properties similar to the current halon, dich lorotrifluoroethane. Theref ore, it was decided that a properly conducted air monitoring e ffort of the current halon would give a good approximation of the exposure levels encountered with the new halon formulation.

A Thermo MIRAN SapphIRe model 205A dis persive infrared spectrophotometer (IR)

was used to determine the levels of the curr ent halon. Levels were logged over several hours while bottles were being filled. T he analyzer’s on-board library includes this halon. The instrument is factory calibrat ed annually. Sissy Clark, the area supervisor, was contacted, and the bottl e filling operation and air monitoring plans were discussed with her in detail. Ekerica Bates was the oper ator at the halon filling booth, and she was briefed as to the monitoring of her breat hing zone at the booth during her work.

The booth, shown in the photographs below (and showing the analyzer probe on Will’s left), has a large (~1.5 square meter) front door that slides up when the transfer and filling operation takes place, which is roughl y about every two minutes with the five pound bottles. The operator bends forward with the upper body fully inside the booth during the task. The door is then slid down and closed duri ng the filling process, which takes place on a shaker table. The filling booth has numerous small openings to allow cables, gas lines, etc. access, and the analyzer probe was inserted through one of30 

## D IRECT 

## CIH

these openings in the ceiling. Because of the openings there was a background level of the halon of about three ppm in the imm ediate area before operations even began for the day. The probe from the analyzer was genera lly within one foot of Ms Bates face during her work with the door open; she is diminutive, and the probe could have been

several inches lower.

The analyzer performs two analyses per sec ond. After startup it was zeroed and warmed up for about 1⁄2 hour prior to logging . The logging setup took one averaged data point every minute, after every 120 analyses. Two periods of time were selected from the data, covering bet ween one and two hours before, and then after lunch. The data were graphed as concentration over time, with annotations giving average and maximum values and changes in activity w hen they took place. The graphs are presented below. There were several high concentration spikes over the logging period. It is speculated that the gas line connection may occasionally be released prior to complete valve closure to cause th is, but there may be another explanation.

The average concentration over the logged in tervals was about seven to eight ppm, with a maximum of at least 50 ppm. Higher values were indicated, but the analyzer was set to identify levels only up to about 15 ppm. Discussions with Bob Francis of Thermo

Scientific about this indica ted that the analyzer has no significant drop-off in accuracy

until it exceeds about 50% of the set range; beyond th at, concentrations may be inaccurate, so this data has been disregarded. Note that these values are from inside the booth, and the operat or only spent part of her time there.

Please feel free to contact Direct CIH if you have any questions regarding this work.

Sincerely,

Lindsay R. Hill, CIH Principal, Direct CIH LLC31 

## D IRECT 

## CIH32 

## D IRECT 

## CIH33 

## D IRECT 

## CIH

0 2 4 6 8 10 12 14 16 189:179:219:259:299:339:379:419:459:499:539:5710:0110:0510:0910:1310:1710:2110:2510:2910:3310:3710:4110:4510:4910:5310:5711:0111:05partspermillion



# time dichlorotrifluoromethane levels at halotron I fill

station, dept. 04, morning

background level 3 max 16

filling 5 lb avg level34 

## D IRECT 

## CIH35 

## D IRECT 

## CIH

May 9, 2013

Will Yarbrough, Safety Director Fred Goodnight, VP Engineering

Amerex Corporation 7595 Gadsden Highway

Post Office Box 81 Trussville, Alabama 35173-0081

Continuing Evaluation: Expos ure of Personnel to Halotron I, Fill Station, Dept. 04

On May 1 st and 2 nd , 2013, Lindsay Hill, an indus trial hygienist with Direct CIH , revisited the Amerex facility in Trussville, Alabama to further investigate exposures initially

monitored last March 13 th . At that time a portable IR analyzer was used for several

hours to determine concentrations of an exti nguishing agent inside the fill booth. As described in the report of March 25 th , the operator enters the boot h every few minutes in order to change out extinguisher bottles in t he filling process. The monitoring results were unexpected. There were higher t han expected background and average levels present, and occasional concentration spikes beyond the range of the analyzer setting. The monitoring event left several questions a bout acquiring a repres entative measure of employee exposure, such as:

What was the proportion of time spent inside the booth vs outside? How far from the booth did the operator go, and did that influence exposure? What was the averaged exposur e, from both inside and out? What was the origin of the background Halotron levels?

Was there a difference in Halotron leve ls based on type of bottle being filled?

This report attempts to answer these questi ons, and present a reasonable estimate of average exposure levels over a 10 hour shift for those working at the fill booth.

To determine the level of Halotron I exposure throughout the course of the shift, it was first necessary to find out what proportion of time is spent inside the booth vs outside. Over two 15 minute intervals on two days a stopwatch was used (discreetly) and the percentage of each period inside vs outside wa s calculated. T he percentages of the two were then averaged. If the employee is not distur bed the proportions are very consistent; 7% of the time at the station is spent with the door open, and the remaining

93% with the door closed. Note that this was measured during the filling of 11 lb.

bottles.36 

## D IRECT 

## CIH

The issue of employee movement away fr om the station and the subsequent change in exposure levels is also dependent on bottle size. The fill stati on operator has two rest breaks, lunch, and bathroom breaks during the shift like every other employee. The only other regular cause to leave the fill st ation is to get additional parts, which are about 20 feet away. Sissy Clark, the area super visor, was asked what amount of time was spent during a 10 hour shift on this ta sk. She estimated perhaps 15 minutes with the large bottles and up to (but probably less than) one half hour with the small bottles, since they need replacements more frequently. This is consistent with the industrial hygienist’s observation. Though momentary and infrequent concentration spikes at the fill booth raise the average slightly in that im mediate area, the proportion of time spent at any substantial distance getting parts is about 2% to 4% of the shift. Even if a concentration spike occurs during the moment t he employee is away, in most cases it is inconsequential to her overall exposure.

To estimate the overall exposure level of t he fill booth operator, about nine hours of air monitoring was logged on May 1 st and 2 nd , with about 6.5 hours logged immediately outside the booth in the worker’s breathing zone, and about 2.5 hours logged inside the booth. The logged data were graphed, annota ted, and are present ed below. Large fans were operating continuously, each betw een about 10 and 20 feet from the door of the fill booth, and located oppos ite one another so that blow ing air converged on the operator’s work area. As a result, even w hen the fill booth door was open the intake at the analyzer probe was buffeted with air from outside the i mmediate area. Using the 7% vs 93% proportions described above, and t he averages from the logs, the average

concentration was calculated as follows:

93% X 0.3 ppm + 7% X 27.6 ppm = 2.21 ppm average from inside and out.

The logged readouts from t he IR analyzer present mini mum, maximum, and average values for every analysis, that is, every 0.5 seconds. All values used here are the maximum values, as they are the most c onservative and if in error will be in the direction producing the safest response or c ontrol. This makes the momentary maxima (the big peaks on the graph) look much greate r than if average or minimum values had been used, but does not appreciably affect the long-term average.

It was suggested that the background levels of Halotron I indicated by the IR analyzer were not from the product at the fill booth; rather, that they originated nearby where a chemically similar halon extinguisher is kept. Because the IR frequencies use the bond energies in a molecule to identify unknow ns, cross sensitivities can occur with compounds that have similar func tional groups, i.e., the same principal bonds. In an effort to avoid this problem , the analyzer takes advantage of the fact that IR absorbance takes place at several, or even hundreds, of specific frequencies, depending on the compound and its interatomic bonds. For mo st of the compounds in the on-board library there are multiple frequencies from wh ich to choose, so that if other compounds37 

## D IRECT 

## CIH

present have absorption frequencies at or near those of the species of interest another frequency can be chosen. For Halotron I there are three frequencies to choose from. Some are not as sensitive as others, but all were tried in an effort to see if a cross sensitivity might be present. Unfortunately it does not appear that this answered the problem. Because of the high concentration spikes encountered earlier, the instrument was adjusted to a less sensitive setting in order to accurately measure Halotron I concentrations during this monitoring. Bec ause of this, the limit of detection was

between one and two orders of magnitude higher than previo usly, so that one cannot say with certainty if the lowest values are below the 3 ppm background identified before. This will be addressed during other work to be done at Amerex over the week of May

21 st , by monitoring in the vicinity of the other halon product.

One other question dealt with t he potential differences in levels of Halotron I when different size bottles were being filled, and if it might be signi ficant. Monitoring conducted in March was almost all during the filling of the small bottles, and the average concentration was much lower, about 10 ppm vs 28 ppm for the large bottles in May. Several variables are in play. The small bo ttles fill considerably faster, so that the operator enters the booth and disconnects and c onnects the line more often. Therefore the time inside the booth is greater, and the po tential for the fill line connection to leak is greater also. Alternately, the operator spends about twice as much time away from the fill booth area getting parts when filling the small bottles as the large ones.

There is no immediate answer here, and it c an only be found when the specific cause of the concentration spikes is identified. Robert Fisher, currently in Safety & Health at the facility but previously a worker at the fill booth, said that the rubber O rings at the bottle connection often lost their seal momentarily while he was filling them. On one occasion on May 2 nd , at the end of the afternoon monitori ng shown on the graph at about 1:35, the concentration on the analyzer was seen to exceed 250 ppm just one or two seconds prior to the end of the automated fill sequence. Perhaps the pressure at this point in the filling process is enough to occasionally overcome the capacity of the O rings. If so, this can be corrected through mechanical or electronic adjustment.

Please feel free to contact Direct CIH if you have any questions regarding this work.

Sincerely,

Lindsay R. Hill, CIH Principal, Direct CIH LLC38 

## D IRECT 

## CIH39 

## D IRECT 

## CIH40 

## D IRECT 

## CIH