SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0 127 Easton, PA 18040 Fax: 610.438.8307

Cutting edge solutions to eliminate health & safety risks



## EXECUTIVE SUMMARY Spray Polyurethane Foam Ventilation Research Project Phase 2

- Industrial Hygiene Monitoring 10 air changes per hour

Prepared For : Heather Palfrey American Chemistry Council Center for the Polyurethanes Industry 700 2nd Street NE Washington, DC 20002

Prepared By :

Brent Altemose, CIH, CSP SABRE Health & Safety, LLC 1015 Zucksville Road Easton, PA 18040

Report Date: December 19 , 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 2 of 6 Fax: 610.438.8307 

### Background

I ndustrial hygiene air monitoring w as conducted in support of the Spray Polyurethane Foam (SPF) Ventilation Research Project, on behalf of the American Chemistry Council (ACC) Center for the Polyurethanes Industry (CPI). The research plan for this project i s detailed in the May 2011 CPI SPF Ventilation Research Proposal. The purpose of this research is to evaluate the impact of changes in ventilation rates on the concentration of chemical vapors and particulates emitted during SPF application.

Emissions fro m three SPF formulations were evaluated: a low density (1/2

- pound) high pressure SPF
, a medium

- den sity (2

- pound) high pressure SPF , and a low

- pressure, two

- component SPF kit. These three generic formulations were developed in Phase I of the project to ensu re they were representative of formulations currently available in the SPF marketplace

. The dates of the emission testing and the composition for each formulation are shown in Table 1.

Table 1 : Generic SPF Formulations

– Composition and monitoring dates (10 air changes per hour)

L ow D ensity (1/2 pound) High Pressure SPF Formulation Medium D ensity (2 pound) High Pressure SPF Formulation Low Pressure (2 Component) Kit Formulation Air monitoring dates July 23 and 24, 2012 May 7 and 8, 2012 September 10 and 11, 2012

A

- side composition

100% p MDI 100% p MDI 100% p MDI

B

- side composition Polyether Polyol (34%) NPE Emulsifier (11.9%) Aromatic Polyester Polyol (36.39%) Aromatic Amino Polyether Polyol (33.61%) Polyester Polyol (23%) Polyether Polyol (23%)

Blowing agent Water (20%) Blowing agent HFC

- 245 f a (6.97%) Water (2.53%) Blowing agent HFC

- 134a (17%)

Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate (TCPP) (25.2%) Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate (TCPP) (15.91%) Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate (TCPP) (30%) Silicone Surfactant (0.7

- 1.0%) Silicone Surfactant (1.0) Silicone Surfactant (2%) Catalyst Bis (2

- Dimethylaminoethyl) ether ( BDMAEE ) ( 0

. 9 %) Tetramethyliminobispropylamine (TMIBPA) ( 2.0

- 3.0%) N,N,N

- Trimethylaminoethyl

ethanolamine (TMAEEA) (4 .0%) Catalyst Bis (2

- Dimethylaminoethyl) ether BDMAEE (0.7 %) Bis (dimethylaminopropyl) methylamine (DAPA) (2.59%) N,N,N

- Trimethylaminoethyl

ethanolamine (TMAEEA) (0.3%) Catalyst Pentamethyldiethylenetriamine (ethylhexanoic, 2

- , potassium salt/ Oxybisethanol, 2,2’) (PMDETA) (5%)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 3 of 6 Fax: 610.438.8307 The test chamber was 7’9’’ x 7’9” x 8’2’’ (490 cubic feet) with a ventilation rate of 85 cubic feet per minute, or 10.4 air changes per hour assuming pe rfect air mixing. Air flow was perpendicular to the worker and the spray application. The worker applying each SPF formulation wore portable sampling pumps with the sampling media placed in the vicinity of the worker’s breathing zone. Area samples were loc ated several feet behind the applicator, at a height of approximately 6.5 feet. After approximately 15 minutes of spray time, the applicator exited the test chamber and the personal and area samples were retrieved. The sprayed cardboard inserts were left i nside the test chamber. A second set of “post

- spray” area samples were collected for one hour beginning 30 m inutes after spraying stopped. After the second set of area samples were completed, the sprayed cardboard inserts were removed and the test chamber was allowed to “air

- out” for two hours before starting another test run. A total of four runs were completed across two days for each of the three generic SPF formulations.


### Air Sampling Results
The detailed results of the air monitoring are presented in our three previous reports, attached to this summary as Appendix A. A discussion of the results for each analyte follows. Our quality control of these samples included field blanks submitted for e ach type of media and an assessment of flow variability and breakthrough, as noted in the reports in Appendix A.

MDI The concentrations of 4,4’

- methylene bisphenyl isocyanate (4,4’

- MDI) exceeded its occupational exposure limit (OEL) during spraying of both the low and medium density SPF formulations (0.011 to 0.037 parts per million or ppm), but not during spraying of the kit formulation (0.0012 to 0.004 ppm). The concentrations of 4,4’

- MDI, 2,4’

- MDI, and polymeric MDI (pMDI) were highest during spraying o f the medium density formulation, next highest during spraying of the low densi ty formulation, and lowest during spraying of the kit formulation.

For all three formulations, MDI was not detected during the post

- spray sampling period, 30 to 90 minutes after spraying stopped, with the SPF still inside the test chamber. The limits of
qua n tit ation for 4,4’

- MDI and 2,4’

- MDI were 0.00014 to 0.00021 p pm, while the limit s of
qu an t itation for pMDI was 0.0 4 0 to 0.0 65 milligrams per cubic meter (mg/m 3 )

.

C atalyst ( Amines)
As shown in Table 1, the type and percentages of amines present in the B side varied for each formulation. BDMAEE is the only amine that was present in any of the formulations that has an established OEL.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 4 of 6 Fax: 610.438.8307 The low and medium density formulations c ontained BDMAEE at 0.7 to 0.9%, respectively, and during spraying the applicator exposure and area concentrations exceeded the OEL ( concentrations were 0.40 to 2.42 ppm for the low density and 0.63 to 3.2 ppm for the medium density ) . During the post

- spray periods, the concentrations were still above the OEL , however, the concentrations for the low density (0.16 to 1.04 ppm) were generally higher than the concentrations for the medium density (below detection, <0.039, to 0.44 ppm).

TMAEEA was also present in both the low and medium density formulations, although only at 0.3% in the medium density compared to 4.0% in the low density. For the medium density

, TMAEEA was not detected in the air either during spraying or during the post

- s pray period ( quantitation limits were 0.053 to 0.257 ppm depending on sample times). For the l ow density, TMAEEA was detected up to 0.52 ppm. During the post

- spray period for the low density

, TMAEEA was only detected during one of four runs, at 0.24 ppm.

DA PA was also present in the medium density formulation at 2.59% and was detected both during spraying (0.93 to 6.74 ppm) and during the post

- spray period (up to 0.08 ppm).

TMIBPA was also present in the low density formulation at 3.0% but was not detected in any of the samples, spraying or otherwise.

PMDETA was the only amine in the kit formulation. During spraying the concentrations were 1.01 to 3.77 ppm. During the post

- spray period, the concentrations were 0.07 to 0.5 ppm.

Fire Retardant (TCPP)

TCPP was the fire retardant in all three formulations, between 15.9 to 30% in the B side. Of the three formulations, t he medium density yielded the highest concentrations during spraying (0.16 to 0.39 ppm), followed by the low density (0.12 to 0.24 ppm), and wi th the kit yielding the lowest concentrations (0.02 to 0.16 ppm). The low density was highest during the post

- spray period (0.0036 to 0.0075 ppm), followed by the medium density (0.0018 to 0.0061 ppm), and with the kit again generally yielding the lowest c oncentrations (0.002 to 0.0034 ppm).

Blowing agents A hydro flu o rocarbon blowing agent was used in the B side for the medium density (HFC

- 245fa) and kit (HFC

- 134a) formulations. The low density formulation used water as the blowing agent.

During spraying of the medium density formulation, the concentrations for HFC

- 245fa were between 186 to 599 ppm. The concentrations were over the OEL for HFC

- 245fa during 3 of 4

runs. During the post

- spray sampling period for this formulation, all samples were non

- detect , at less than 5 pp m, which is well below the OEL

.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 5 of 6 Fax: 610.438.8307 During spraying of the kit formulation, the concentrations for HFC

- 134a were between 5,000 to 11,000 ppm, which is over its OEL . During the post

- spray sampling period for this formulation, all of the samples were between 188 to 590 ppm, which is below the OEL

.



### Conc l u sions Three SPF formulations were sprayed for 15 minutes in a 490 cubic foot chamber with 10.4 air changes per hou r of general ventilation perpendicular to the spray. Breathing zone and area concentrations were measured during spraying, and were generally similar for all of the chemical vapors and particulates measures. Area concentrations were also measured for the p eriod 30 to 90 minutes after the spray.

During spraying, the concentrations of 4,4’

- MDI were over its OEL for the low and medium density formulations, and were detectable but below the OEL for the kit formulation. MDI was not detected during the post

- spra y period for any of the formulations.

The concentrations of an amine, BDMAEE, were over its OEL during spraying of the low and medium density formulations. At times, the concentration of BDMAEE was still over its OEL during the post

- spray testing. BDMAEE was not present in the kit formulation, but another amine, PMDETA, was detected during spraying at concentrations similar to those observed for BDMAEE. Some of the other amines present in the formulations were also detectable in the air during the spray an d post

- spray periods.

The fire retardant, TCPP , in all three formulations was detected in the air during the spray and post

- spray periods, but at concentrations one to two orders of magnitude (approximately 10 to 100 times) lower during the post

- spray tes ting.

The blowing agents in the medium density and kit formulations ( HFC

- 245fa and HFC

- 134, respectively) were above their OEL s during spraying, but below their limits during the post

spray testing.

These results indicate that during application of thre e generic SPF formulations with 10 air changes per hour general ventilation, OELs were exceeded and respiratory protection is needed. Also, d uring the time period 30 to 90 minutes after spraying was stopped , OELs were at times exceeded. For these formulati ons at 10 air changes per hour, more than 90 minutes may be required in order to enter the area without respiratory protection.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 6 of 6 Fax: 610.438.8307 

### APPENDIX A REPORTSSABRE Health & Safety www.sabresafety.net

1015 Zucksv ille Road Phone: 866.734.0127 Easton, PA 18040 Fax: 610.438.8307

Cutting edge solutions to eliminate health & safety risks



## I NDUSTRIAL HYGIENE MONITORING SPF Ventilation Research Project

Prepared For : Heather Palfrey American Chemistry Council Center for the Polyurethanes Industry 700 2nd Street NE Washington, DC 20002

Prepared By :
SABRE Health & Safety, LLC 1015 Zucksville Road Easton, PA 18040

Monitoring Dates: May 7

- 8 , 2012 Report Date: June 22 , 2012 Report Revised: February 8, 2013SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 2 of 12 Fax: 610.438.8307 

### Background

This monitoring was conducted in support of the Spray Polyurethane Foam (SPF) Ventilation Research Project, on behalf of the American Chemistry Council (ACC) Center for the Polyurethanes Industry (CPI). The research plan for this project is detailed in the May 2011 CPI SPF Ventilation Research Propo sal. The purpose of this research is to evaluate the impact of changes in ventilation rates on the concentration of chemical vapors and particulates emitted during SPF application. The same chemicals were evaluated beginning 30 minutes after spraying
to as sess the rate at which decreases in th e airborne concentrations occur. Chemical ingredients selected for evaluation represent those typically present in SPF formulations and vary with each formulation tested throughout the project. Substances to be evaluat ed include: Methylene diphenyl diisocyanate (MDI), amine catalysts, blowing agents other than water, and flame retardants.

The first set of four runs occurred on May 7 and 8, 2012. The formulation for these four runs

was medium

- density (2

- pound) high pres sure SPF. The specific chemicals monitored in this formulation are shown in Table 1. The A and B sides were sprayed at a one to one ratio by volume. Table 2 shows the spray parameters. Data were not available on some spray parameters for the first run, due to a problem with the spray equipment. The session times show n are the approximate times spent by the applicator inside the test chamber.

Table 1

. Medium D ensity (2 pound) High Pressure SPF Formulation

A

- side

100% p MDI

B

- side

Aromatic Polyester Polyol (36.39%) Aromatic Amino Polyether Polyol (33.61%)
Blowing agent HFC

- 245fa (6.97%) Water (2.53%)

Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate ( TCPP ) (15.91%)
Silicone Surfactant (1.0%) Catalyst Bis (2

- Dimethylaminoethyl) ether (BDMAEE) (0.7 %) Bis (dimethylaminopropyl) methylamine (DAPA) (2. 59%) N,N,N

- Trimethylaminoethylethanolamine ( TMAEEA ) (0

. 3 %)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 3 of 12 Fax: 610.438.8307

Table 2. Spray Parameters , Medium D ensity (2 pound) High Pressure SPF Formulation

Run
No. Date Average density (lb/ft 3 ) Number of

inserts sprayed Quantity of B

side sprayed (grams) Total session

time (minutes: seconds)

1 5/7/2012 AM Not recorded 6 Not recorded Approximately

7:00

2 5/7/2012 PM 1.83 12 9,350 14:55

3 5/8 /2012 AM 1.88 12 10,966 18:10

4 5/8 /2012 PM 1.85 12 10,931 15:30



### Exposure Limits

Table 3 shows the exposure rating system used to categorize the air sampling results, based on the system recommended by the American Industrial Hygiene Association. Table 4 shows the
exposure limits for the chemicals assessed in this report. For a key to these and all of the data tables, please see the key at the end of this rep ort, prior to Tables 5 through 8

. Table 3. Exposure Ratings

Rating* Description Actual or Estimated Exposure

0 Trivial < 0.01 x OEL

1 Highly controlled 0.01 to 0.1 x OEL

2 Well controlled 0.1 to 0.5 x OEL

3 Controlled 0.5 to 1 x OEL

4 Poorly controlled >1 x OEL

5 Very poorly controlled >50 x OEL

*Ratings based on “A Strategy for Assessing and Managing Occupational Exposures”, 2006, 3 rd edition. American Industrial Hygiene Association, Fairfax, VA. (trivial and very poorly controlled categories added)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 4 of 12 Fax: 610.438.8307 Table 4. Occupational Exposure Limits

CAS Analyte Occupational Exposure Limit Type of OEL (e.g.

OSHA Ceiling, ACGIH TLV, NIOSH REL) OEL (units)

101

- 68

- 8 Methylene bisphenyl

isocyanate (MDI) 0.02

0.005 OSHA Ceiling

ACGIH TLV

- TWA ppm

ppm

460

- 73

- 1 1,1,1,3,3

-

Pentafluoropropane ( HFC

- 245fa ) 300 AIHA WEEL p pm

3033

- 62

- 3 Bis (2

-

Dimethylaminoethyl) ether (BDMAEE) 0.05

0.15 ACGIH TLV

- TWA

ACGIH TLV

- STEL ppm

ppm



### Air Sampling Methods

A worker applying SPF wore portable sampling pumps with the sampling media placed in the vicinity of the worker ’s b reathing zone. Area samples were located several feet behind the applicator, at a height of approximately 6.5 feet. After approximately 15 minutes of spray time, the applicator exited the test chamber and the personal and area samples were retrieved. The sprayed cardboard inserts were le ft inside the test chamber. A second set of “post

- spray” area samples were collected for one hour beginning 30 minutes after spraying stopped

. After the second set of area samples were completed, the sprayed cardboard inserts were removed and the test cha mber was allowed to “air

- out” for two hours before starting another test run. Before each run, the air in the test chamber was cleared with a real

- time instrument calibrated for the blowing agent (HFC

- 245fa). No HFC

- 245fa was detected in the chamber prior to starting any run. For more detail on the air sampling metho dology, please see Appendix A of this report and the May 2011 ACC CPI research plan. A photograph of a typical configuration of the samples is shown in Appendix B.

Our quality control of these samples included field blanks submitted for each type of media and an assessment of flow variability and breakthrough. No issues were observed in terms breakthrough (oversaturation) of the sampling media. Some issues were obser ved with flow variability and field blanks, as described in the following paragraphs and as noted in the data tables.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 5 of 12 Fax: 610.438.8307 For MDI and pMDI , nothing was detected on the blanks, including the blind blank, and there was little breakthrough to the filters (some 4,4

- MDI was detected on many of the filters sampled during spraying, but always at less than 5% of the amount detected in the impinger s ample). The only issue was flow variability, which we believe may have been due to int erference by the toluene with the pumps used. Four of the samples had 10

- 20% change in flow during the sampling, and 2 samples had 26

- 40% variability. A comparison of the results for these samples to the results for samples that did not have flow variability issues indicates that this issue did not substantially affect our results. Future samples will use specially configured pumps to avoid these issues.

For the amines , l ittle br eakthrough (less than 7%) was observed on the tubes, and the flow variability was generally low (10 of 12 were less than 10%, the other two were 17 and 24%). No amines were detected on three field blank s and a lab blank

. For the blowing agent , not hing was detected on two field blanks. However, some overspray was observed on the applicator's samples, particularly during runs 2 through 4, so the applicator samples may have been biased high. This issue will be address ed with badge filter covers for fu ture runs

.
For the fire retardant, t here was one area sample during spraying that was inv alid. The results came back non

- detect, and for this sample the industrial hygienist noted in the field a possible pump problem. TCPP was not detected on two field bl anks, and no breakthrough or flow variability in excess of 10% were noted.


### Air Sampling Results
Tables 5 through 8 show the results of our industrial hygiene air sampling. A discussion of the results for eac h analyte follows

.

MDI

As shown in Table 5

, the levels of MDI were far over its exposure limit during spraying. The applicator and area results during spraying were similar during each run (+/

- 36%) and varied by about a factor of 2 across the four runs. 2,4

- MDI ranged from 0.0030 to 0.0058 ppm; 4,4

- MD I ranged from 0.019 to 0.03 7 ppm; and pMDI ranged from 0.17 to 0.41 mg/m 3 . All three were

non

- detect during the post

- spray sampling period (limit s of detection ranged from 0.0 4 4 to 0.0 65 mg/m3 for pMDI or 0.00014 to 0.00021 ppm for 2,4

- MDI and 4,4

- MDI ).SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 6 of 12 Fax: 610.438.8307 C atalyst (Amines)

As shown in Ta ble 5, the levels of BDMAEE were far over its exposure limit during spraying. For both BDMAEE and DAPA , the area samples were consistently higher than the applicator samples during spraying. The area samples were 11 to 68% greater, with outlier s that were 2.2 and 2.7 times greater during the first run for BDMAEE and DAPA, respectively. Notably

, the first run had an abbreviated run time and the exposure time for the applicator was limited . There

were also amines detected during the purge (30

- 90 minutes afte r spraying) . BDMAEE was detected during runs 2 through 4, and the concentrations were 0.084, 0.051, and 0.44 ppm , which

are still over its exposure limit . DAPA was only detected during the purge for runs 2 and 3 , at 0. 08 ppm each time

. TMAEEA was not detected in any of the samples, spraying or otherwise.

Fire Retardant (TCPP)

As shown in Table 6, during spraying TCPP concentrations were 0.16 to 0.37 ppm for the applicator and 0.29 to 0.39 ppm for the area sample. One of the four area samples during spraying was invalid due to a pump failure. T he area concentrations were higher than the applicator exposures for 2 of 3 other runs

. During the post

- spray sampling period , TCPP concentrations were 0.0018 to 0.0061 ppm.

Blowing agent ( HFC

- 245fa )

As shown in Table 7, the concentration s for HFC

- 245fa were also generally over its exposure limit during spraying , except during the first run when the spray time was truncated

. T he applicator exposures ranged from 186 to 599 ppm (365 to 599 ppm if you o mit the first, shorter run). The area samples during spraying ranged from 281 to 365 ppm. The area sample was higher than the applicator sample during run 1, but lower during runs 2 through 4. Because protective covers for the passive sampling badges were not available at the time of sampling, some overspray may have collected on the applicator samples and caused these samples to read higher than the actual exposure. This would also explain why in general only the blowing agent concentrations were higher fo r the applicator, compared to the area samples. During the post

spray sampling period , all of the samples were non

- detect, at less than 5 ppm

.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 7 of 12 Fax: 610.438.8307 

### Conc l u sions

The concentrations of MDI and BDMAEE were well over their exposure limits during the application of spray polyurethane foam for 15 minutes in a chamber with 10 air changes per hour. The concentration of HFC

- 245fa was also generally over its exposure limit. Furthermore, the concentration of BDMAEE was also ove r its exposure limit during the post

- spray sampling period (30 to 90 minutes after spraying) for 3 of 4 runs.


### Revision History

2/8/2013

– Quantitation (also referred to herein as detection) limits for pMDI revised.



### Key to Tables

The following is a key to abbreviations and notes on the tables.

*= flow variation between pre

- and post

- calibration was between 10

- 20% **= flow variation between pre

- and post

- calibration was between 20

- 40% mg/ m3 = milligrams per cubic meter ppm = parts per million
L = Liters
min = minutes ug = micrograms Lpm = Lite rs per minute
OEL = Occupational Exposure Limit OSHA PEL = Occupational Safety and Health Administration Permissible Exposure Limit ACGIH TLV = American Conference of Governmental Industrial Hygienists Threshold Limit Values AIHA WEEL = American Industrial Hygiene Association Workplace Environmental Exposure Levels TWA = time weighted average, adjusted to eight hours STEL = short term exposure limit, over 15 minutes ach = air changes per hour n/a = not applicableSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 8 of 12 Fax: 610.438.8307 Table 5

. MDI Results, Medium Density (2 pound) High Pressure SPF Formulation, 10 ach, May 7

- 8, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 9 of 12 Fax: 610.438.8307 Table 6

. Amine Results, Medium Density (2 pound) High Pressure SPF Formulation, 10 ach, May 7

- 8, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 10 of 12 Fax: 610.438.8307 Table 7

. TCPP Results, Medium Density (2 pound) High Pressure SPF Formulation, 10 ach, May 7

- 8, 2012

Table 8

. HFC

- 245fa Results, Medium Density (2 pound) High Pressure SPF Formulation, 10 ach, May 7

- 8, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 11 of 12 Fax: 610.438.8307 

### APPENDIX A SAMPLING METHODS

This section describes the methods used to monitor for the chemicals during SPF application. For more detail, please see the May 2011 ACC CPI research proposal.

SKC Aircheck 52 (Model 224

- 52) and SKC AirLite pumps were used for active sampling. The calibr ation of e ach pump was verified using a primary flow standard

. The samples were analyzed by the laboratories and methods shown in Table A1

.

Table A1 : Air Sampling and Analytical Methodology for Select SPF Constituents.

CAS # Analyte Analytical Laboratory
and Method Flow
Rate Sampling media and limit of
detection.

101

- 68

- 8 Methylene bisphenyl isocyanate

(MDI) Bayer; HPLC with UV Detection; BMS IH Laboratory Method
Nos: 1.20.0 and 1.7.7 1.0 Lpm Midget impinger with 15 mL toluene / 1

- (2

- pyridyl) piperazine, followed by: 13 mm glass fiber filter treated with 1

- (2

- pyridyl) piperazine and diethyl phthala te housed in a Swinnex cassette, field extracted with 90/10 (v/v) acetonitrile/dimethylsulfoxide 9016

- 87

- 9 Polymeric MDI (pMDI)

(3

- ring and larger o ligomers of MDI)

460

- 73

- 1 1,1,1,3,3

- Pentafluoropropane

(HFC 245

- a) Assay Technology; Modified OSHA 7 N/A Diffusive sampler

– Assay Technology Sampler No.548

13674

- 84

- 5 Tris

- (1

- chloro

- 2

- propyl) phosphate

(TCPP) Bureau Veritas; GC/NPD ICL

- IP Method No GC 024

- 1 1.0 Lpm XAD

- 2 tubes ; SKC 226

- 30

- 16

3033

- 62

- 3 Bis (2

- Dimethylaminoethyl) ether

(BDMAEE) Bayer ; Bayer Method
No. 2.10.3
, d esorption with acetone and analyzed by GC/NPD 0.50 Lpm XAD

- 2 tubes; SKC 226

- 30

- 06

2212

- 32

- 0 N,N,N

- Trimethylamino

ethylethanolamine ( TMAEEA )

3855

- 32

- 1 Bis (dimethylaminopropyl) methylamine (DAPA)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 12 of 12 Fax: 610.438.8307 

### APPENDIX B PHOTOGRAPH

Figure B1. SPF Application Sampling LocationsSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Fax: 610.438.8307

Cutting edge solutions to eliminate health & safety risks



## I NDUSTRIAL HYGIENE MONITORING SPF Ventilation Research Project

Prepared For : Heather Palfrey American Chemistry Council Center for the Polyurethanes Industry 700 2nd Street NE Washington, DC 20002

Prepared By :
SABRE Health & Safety, LLC 1015 Zucksville Road Easton, PA 18040

Monitoring Dates: July 23

- 24, 2012 Report Date: August 31, 2012 Revised Date: February 8, 2013SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 2 of 12 Fax: 610.438.8307 

### Background

This monitoring was conducted in support of the Spray Polyurethane Foam (SPF) Ventilation Research Project, on behalf of the American Chemistry Council (ACC) Center for the Polyurethanes Industry (CPI). The research plan for this project is detailed in the May 2011 CPI SPF Ventilation Res earch Proposal. The purpose of this research is to evaluate the impact of changes in ventilation rates on the concentration of chemical vapors and particulates emitted during SPF application. The same chemicals were evaluated beginning 30 minutes after spr aying
to assess the rate at which decreases in th e airborne concentrations occur. Chemical ingredients selected for evaluation represent those typically present in SPF formulations and vary with each formulation tested throughout the project. Substances to be evaluated include: Methylene diphenyl diisocyanate (MDI), amine catalysts, blowing agents other than water, and flame retardants.

The first set of four runs occurred on May 7 and 8, 2012 , a s detailed in our previous report dated June 22, 2012

. The for mulation for those four runs was medium

- density (2

- pound) high pressure SPF. This report details the results of the second set of four runs which occurred on July 23 and 24, 2012. The formulation for these four runs was low

- density ( 1/ 2

- pound) high pressur e SPF. The specific chemicals present in this formulation are shown in Table 1. The A and B sides were sprayed at a one to one ratio by volume. Table 2 shows the spray parameters. The session times show n are the approximate times spent by the applicator in side the test chamber.

Table 1

. Low Density ( 1/2 pound ) High Pressure SPF Formulation

A

- side

100% p MDI

B

- side

Polyester Polyol (34%) Blowing agent W ater (20 %)
Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate ( TCPP ) (25.2 %)

Silicone Surfactant (1.0%) Catalyst Bis (2

- Dimethy laminoethyl) ether (BDMAEE) (0.9 %) Tetramethyliminobispropylamine (TMIBPA) (3.0%) N,N,N

- Trimethylaminoethylethanolamine ( TMAEEA ) (4.0 %)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 3 of 12 Fax: 610.438.8307 Table 2. Spray Parameters , Low Density ( 1/2 pound ) High Pressure SPF Formulation

Run
No. Date Average density (lb/ft 3 ) * Number of

inserts sprayed Quantity of B

side sprayed ( pounds ) Total session

time (minutes: seconds) Temperature in

Test Chamber Start/End/Post * *

1 7/23/2012 AM 0.8 12 10 15:00 80 / 93 / 87 0 F

2 7/23/2012 PM 0.8 12 10 15:00 85 / 96 0 F

3 7/24/2012 AM 0.8 12 10 15:00 79 / 93 / 88 0 F

4 7/24/2012 PM 0.8 12 10 15:00 84 / 97 / 90 0 F

* This is the average density measured after shrinkage. Average density of the foam was approximately 0.6 lb/ft 3

. ** Temperature was recorded at the start of spraying, at the end of spraying, and 30 minutes post

- spray (except for run 2). For runs 3 and 4, the temperature 90 minutes post

- spray was also recorded and was equal to the value 30 minutes post

- spray each time.


### Exposure Limits

Table 3 shows the exposure rating system used to categorize the air sampling results, based on the system recommended by the American Industrial Hygiene Association. Table 4 shows the exposure limits for the chemicals assessed in this repo rt. For a key to these and all of the data tables, please see the key at the end of this rep ort, prior to Tables 5 through 7

. Table 3. Exposure Ratings

Rating* Description Actual or Estimated Exposure

0 Trivial < 0.01 x OEL

1 Highly controlled 0.01 to 0.1 x OEL

2 Well controlled 0.1 to 0.5 x OEL

3 Controlled 0.5 to 1 x OEL

4 Poorly controlled >1 x OEL

5 Very poorly controlled >50 x OEL

*Ratings based on “A Strategy for Assessing and Managing Occupational Exposures”, 2006, 3 rd edition. American Industrial Hygiene Association, Fairfax, VA. (trivial and very poorly controlled categories added)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 4 of 12 Fax: 610.438.8307 Table 4. Occupational Exposure Limits (OELs)

CAS Analyte Occupational Exposure Limit Type of OEL OEL (units)

101

- 68

- 8 Methylene bisphenyl

isocyanate (MDI) 0.02

0.005 OSHA Ceiling

ACGIH TLV

- TWA ppm

ppm

3033

- 62

- 3 Bis (2

-

Dimethylaminoethyl) ether (BDMAEE) 0.05

0.15 ACGIH TLV

- TWA

ACGIH TLV

- STEL ppm

ppm



### Air Sampling Methods

A worker applying SPF wore portable sampling pumps with the sampling media placed in the vicinity of the worker ’s b reathing zone. Area samples were located several feet behind the applicator, at a height of approximately 6.5 feet. After approximately 15 minutes of spray time, the a pplicator exited the test chamber and the personal and area samples were retrieved. The sprayed cardboard inserts were left inside the test chamber. A second set of “post

- spray” area samples were collected for one hour beginning 30 minutes after spraying s topped

. After the second set of area samples were completed, the sprayed cardboard inserts were removed and the test chamber was allowed to “air

- out” for two hours before starting another test

run. For more detail on the air sampling metho dology, please s ee Appendix A of this report and the May 2011 ACC CPI research plan. A photograph of a typical configuration of the samples is shown in Appendix B.

Our quality control of these samples included field blanks submitted for each type of media and

an assessme nt of flow variability and breakthrough, as described in the following paragraphs and as noted in the data tables.

For MDI and pMDI , nothing was detected on the field blanks or the lab blanks , and there was no breakthrough to the filters ( no MDI or pMDI was detected on the filters). The only is sue was flow variability, which appeared to be due primarily to the accumulation of MDI inside some of the impingers, particularly those of the “fritted” type

. Two of the samples had 10

- 20% change in flow during the sampling, another had 25% variability, and two samples had very high variability, 54 and 64 %. A comparison of the results for these samples to the results for samples that did not have flow variability issues indicates that while the two samples with 10

- 20% flow variability did not appear to have been affected, the results for the three samples with greater than 20% flow variability all appear to be biased low. That is, the results appear to be lower thanSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 5 of 12 Fax: 610.438.8307 expected. These thre e results, and particularly the two results with very high flow variability, may need to be ignored in any data analysis for the results. Future sampling will not use fritted

type impingers, hopefully eliminating this issue.

For the amines

, no br eakthrou gh was observed on the tubes, and the flow variability was generally low ( all varied less than 8 %). No amines were detected on two field blank s and a lab blank

.
For the fire retardant, TCPP was not detected on two field blanks or the lab blank , and no flo w

v ariability in excess of 10% was noted. Two of samples showed excess breakthrough at 18% and 37%. Excess breakthrough can be an indication of potential sample loss. However, both of the samples with breakthrough were taken during the post

- spray period, a nd a comparison of the results for these two samples to the post

- spray period for the other two runs indicates the results were similar and sample loss was most likely not a significant impact on the results.


### Air Sampling Results
Tables 5 through 7 show the results of our industrial hygiene air sampling. A discussion of the results for eac h analyte follows

.

MDI

As shown in Table 5

, the applicator’s exposure to 4,4

- MDI during the spray period was over the exposure limit

. The applicator results during spraying were 0.0020 to 0.0038 ppm for 2,4

- MDI, 0.011 to 0. 020 ppm for 4,4

- MDI , and 0.11 to 0.18 mg/m 3 for pMDI

. Three of the four area samples during spraying were below the exp osure limit. H owever , two of these samples showe d very high flow variability which may have biased the results. The area sample during spraying for the fourth run, which did not have an issue with flow variability, was greater than the exposure limit and the applicator exposure. All three MDI analytes w ere non

- detect during the four post

- spray sampling period s. L imits of detection were 0.0 4 3 to 0. 049 mg/m 3 for pMDI or 0.00016 ppm for 2,4

- MDI and 4,4

- MDI.

C atalyst (Amines)

As shown in Ta ble 6

, the applicator’s exposure to BDMAEE was 0.75 to 1.45 ppm during spraying, which is far over its exposure limit

. The applicator’s exposure to TMAEEA during spraying was 0.30 to 0.41 ppm. For both BDMAEE and TMAEEA, the area samples were generally higher than the applicator samples during spraying , on 3 of 4 runs

. BDMAEE concentrations in the area samples during spraying ranged from 0.40 to 2.42 ppm , while TMAEEA ranged from non

- detect to 0.52 ppm

. BDMAEE was detected during the post

- spraySABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 6 of 12 Fax: 610.438.8307 sampling period for all four runs , a t concentrations betwee n 0.16 to 1.04 ppm , which are still over its exposure limit

. TMAEEA was only detected during the post

- spray period for run 2 , at 0. 24 ppm

. TM IBPA was not detected in any of the samples, spraying or otherwise.

Fire Retardant (TCPP)

As shown in Table 7

, dur ing spraying TCPP concentrations were 0.14 to 0.22 ppm for the applicator and 0.12 to 0.24 ppm for the area sample. During the post

- spray sampling period

, TCPP concentrations were 0.0036 to 0.0075 ppm.



### Conc l u sions

The concentrations of MDI and BDMAEE were well over their exposure limits during the application of spray polyurethane foam for 15 minutes in a chamber with 10 air changes per hour. Furthermore, the concentration of BDMAEE was also ove r its exposure limit during the post

- spray sampling perio d (30 to 90 minutes after spraying) for all four runs. 

### Revision History

2/8/2013

– Quantitation (also referred to herein as detection) limits for pMDI revised.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 7 of 12 Fax: 610.438.8307 

### Key to Tables

The following is a key to abbreviations and notes on the tables.

*= flow variation between pre

- and post

- calibration was between 10

- 20% **= flow variation between pre

- and post

- calibration was 25%

** * = flow variation between pre

- and post

- calibration was between 50

- 65 % +=breakthrough to back section was 18% ++=breakthr ough to back section was 37% mg/ m3 = milligrams per cubic meter ppm = parts per million
L = Liters
min = minutes ug = micrograms Lpm = Liters per minute
OEL = Occupational Exposure Limit OSHA PEL = Occupational Safety and Health Administration Permissibl e Exposure Limit ACGIH TLV = American Conference of Governmental Industrial Hygienists Threshold Limit Values AIHA WEEL = American Industrial Hygiene Association Workplace Environmental Exposure Levels TWA = time weighted average, adjusted to eight hours STEL = short term exposure limit, over 15 minutes ach = air changes per hour n/a = not applicableSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 8 of 12 Fax: 610.438.8307 Table 5

. MDI Results, Low Density ( 1/2 pound ) High Pressure SPF Formulation, 10 ach, July 23

- 24 , 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 9 of 12 Fax: 610.438.8307 Table 6

. Amine Results, Low Density ( 1/2 pound ) High Pressure SPF Formulation, 10 ach, July 23

- 24 , 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 10 of 12 Fax: 610.438.8307 Table 7

. TCPP Results, Low Density ( 1/2 pound ) High Pressure SPF Formulation, 10 ach, July 23

- 24 , 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 11 of 12 Fax: 610.438.8307 

### APPENDIX A SAMPLING METHODS

This section describes the methods used to monitor for the chemicals during SPF application. For more detail, please see the May 2011 ACC CPI research proposal.

SKC Aircheck 52 (Model 224

- 52) and SKC AirLite pumps were used for active sampling. The calibr ation of e ach pump was verified using a primary flow standard

. The samples were analyzed by the laboratories and methods shown in Table A1

.

Table A1 : Air Sampling and Analytical Methodology for Select SPF Constituents.

CAS # Analyte Analytical Laborator y and Method Flow
Rate Sampling media and limit of
detection.

101

- 68

- 8 Methylene bisphenyl isocyanate

(MDI) Bayer; HPLC with UV Detection; BMS IH Laboratory Method
Nos: 1.20.0 and 1.7.7 1.0 Lpm Midget impinger with 15 mL toluene / 1

- (2

- pyridyl) piperazine, followed by: 13 mm glass fiber filter treated with 1

- (2

- pyridyl) piperazine and diethyl phthala te housed in a Swinnex cassette, field extracted with 90/10 (v/v) acetonitrile/dimethylsulfoxide 9016

- 87

- 9 Polymeric MDI (pMDI)

(3

- ring and larger oligomers of MDI)

13674

- 84

- 5 Tris

- (1

- chloro

- 2

- propyl) phosphate

(TCPP) Bureau Veritas; GC/NPD ICL

- IP Method No GC 024

- 1 1.0 Lpm XAD

- 2 tubes ; SKC 226

- 30

- 16

3033

- 62

- 3 Bis (2

- Dimethylaminoethyl) ether

(BDMAEE) Bayer ; Bayer Method
No. 2.10.3
, d esorption with acetone and analyzed by GC/NPD 0.50 Lpm XAD

- 2 tubes; SKC 226

- 30

- 06

2212

- 32

- 0 N,N,N

- Trimethylamino

ethylethanolamine ( TMAEEA )

3855

- 32

- 1 Tetramethyliminobispropylamine (TMIBPA)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 12 of 12 Fax: 610.438.8307 

### APPENDIX B PHOTOGRAPH

Figure B1. SPF Application Sampling LocationsSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Fax: 610.438.8307

Cutting edge solutions to eliminate health & safety risks



## I NDUSTRIAL HYGIENE MONITORING SPF Ventilation Research Project

Prepared For : Heather Palfrey American Chemistry Council Center for the Polyurethanes Industry 700 2nd Street NE Washington, DC 20002

Prepared By :
SABRE Health & Safety, LLC 1015 Zucksville Road Easton, PA 18040

Monitoring Dates: September 10

- 11 , 2012 Report Date: October 24 , 2012 Revised: February 8 , 2013SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 2 of 12 Fax: 610.438.8307 

### Background

This monitoring was conducted in support of the Spray Polyurethane Foam (SPF) Ventilation Research Project, on behalf of the American Chemistry Council (ACC) Center for the Polyurethanes Industry (CPI). The research plan for this project is detailed in the May 2011 CPI SPF Ventilation Res earch Proposal. The purpose of this research is to evaluate the impact of changes in ventilation rates on the concentration of chemical vapors and particulates emitted during SPF application. The same chemicals were evaluated beginning 30 minutes after spr aying
to assess the rate at which decreases in th e airborne concentrations occur. Chemical ingredients selected for evaluation represent those typically present in SPF formulations and vary with each formulation tested throughout the project. Substances to be evaluated include: Methylene diphenyl diisocyanate (MDI), amine catalysts, blowing agents other than water, and flame retardants.

The first set of four runs occurred on May 7 and 8, 2012 , a s detailed in our previous report dated June 22, 2012

. The for mulation for those four runs was medium

- density (2

- p ound) high pressure SPF. This second set of four runs on July 23 and 24, 2012 , as detailed in our previous report dated August 31, 2012

. The formulation for the second set of four runs was low

- density ( 1/ 2

- pound) high pressure SPF.

This report details the results of the third set of runs for a low pressure (2 component) kit formulation, which occurred on September 10 and 11, 2012. The specific chemicals present in this formulation are shown in Table 1.

T able 1

. Low Pressure (2 Component) Kit Formulation

A

- side

92.5% MDI Blowing Agent

– HFC

- 134a (7.5% )

B

- side

Polyester Polyol (23%) Blowing Agent

– HFC

- 134a (17%)

Fire Retardant

- Tris

- (1

- chloro

- 2

- propyl) phosphate TCPP (30%)
Silicone Surfactant (2%) Catalyst

- Pentamethyldiethylenetriamine (PMDTA) (5%)
(ethylhexanoic, 2

- , potassium salt/ Oxybisethanol, 2,2’)SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 3 of 12 Fax: 610.438.8307 Table 2 shows the spray parameters. The session times shown are the approximate times spent by the applicator inside the test chamber. For each run, i.e. for each set of 6 inserts sprayed, two pairs of A and B side cylinders were used. Therefore, a total of 8 pairs of cylinders were used in all. With two exceptions, the calculated ratio of A to B side sprayed were 1.09 to 1.27. For the two exceptions, the ratios were 0.65 and 2.06. In one case, during the first run, the A side was consumed and spraying co ntinued with B side only for one

- half of one insert.

Table 2. Spray Parameters , Low Pressure (2 Component) Kit Formulation

Run
No. Date Average density (lb/ft 3 )* Number

of
inserts sprayed Q uantity

of A side sprayed (lb s) ** Quantity

of B side sprayed ( lb s ) ** Total

session time (minutes: seconds) Temperature in

Test Chamber Start/End/Post

1 7/23/2012 AM 2.41 6 10.8 8.9*** 19:00 72 / 79 / 78 0 F

2 7/23/2012 PM 2.41 6 10.8 8.9 15:00 74 / 84 / 78 0 F

3 7/24/2012 AM 2.41 6 10.8 8.9 18:00 72 / 79 / 76 0 F

4 7/24/2012 PM 2.41 6 10.8 8.9 16:00 73 / 82 / 78 0 F

* This is the average density from five randomly selected inserts across all four runs

. The measured den s i ties ranged from 2.27 to 2.57 lb/ft 3

* *These are the approximate weights of A and B side sprayed based on the total used for all four runs

. ** * For Run 1, approximately 1⁄2 of one insert was sprayed with B side only.


### Exposure Limits

Table 3 shows the exposure limits for the chemicals assessed in this report. Table 4 shows the exposure rating system used to categorize the air sampling results, based on the system recommended by the American Industrial Hygiene Association. For a key to these and all of the data tables, please see the key at the end of this rep ort, prio r to Tables 5 through 8

. Table 3. Occupational Exposure Limits (OELs)

CAS Analyte Occupational Exposure Limit Type of OEL OEL (units)

101

- 68

- 8 Methylene bisphenyl

isocyanate (MDI) 0.02

0.005 OSHA Ceiling

ACGIH TLV

- TWA ppm

ppm

3033

- 62

- 3 1,1,1,2

-

Tetrafluoroethane (HFC

- 134a) 1000 AIHA WEEL ppmSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 4 of 12 Fax: 610.438.8307 Table 4 . Exposure Ratings

Rating* Description Actual or Estimated Exposure

0 Trivial < 0.01 x OEL

1 Highly controlled 0.01 to 0.1 x OEL

2 Well controlled 0.1 to 0.5 x OEL

3 Controlled 0.5 to 1 x OEL

4 Poorly controlled >1 x OEL

5 Very poorly controlled >50 x OEL

*Ratings based on “A Strategy for Assessing and Managing Occupational Exposures”, 2006, 3 rd edition. American Industrial Hygiene Association, Fairfax, VA. (trivial and very poorly controlled categories added)



### Air Sampling Methods

A worker applying SPF wore portable sampling pumps with the sampling media placed in the vicinity of the worker ’s b reathing zone. Area samples were located several feet behind the applicator, at a height of approximately 6.5 feet. After approximately 15 minutes of spray time, the applicator exited the test chamber and the personal and area samples were retrieved. The

s prayed cardboard inserts were left inside the test chamber. A second set of “post

- spray” area samples were collected for one hour beginning 30 minutes after spraying stopped

. After the second set of area samples were completed, the sprayed cardboard inserts were removed and the test chamber was allowed to “air

- out” for two hours before starting another test

run. For more detail on the air sampling metho dology, please see Appendix A of this report and the May 2011 ACC CPI research plan. A photograph of a typical configuration of the samples is shown in Appendix B.

Our quality control of these samples included field blanks submitted for each type of media and an assessment of flow variability and breakthrough, as described in the following paragraphs an d as noted in the data tables.

For MDI and pMDI

, one sample was voided due to a pump failure during sampling, for the sample worn by the applicator during the second run. No MDI or pMDI was detected on the fieldSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 5 of 12 Fax: 610.438.8307 blanks or the lab blanks . F or all samples except one, there was no breakthrough to the filters ( no MDI or pMDI was detected on the filters in all but one case ). The exception was the sample collected on the applicator during the first run. For this sample, the concentration of 4,4

- MDI on the filte r was 18% of the concentration of 4,4

- MDI found in the impinger. While excessive breakthrough can be an indication of sample loss and can indicate that the samples is biased low, we do not believe that to be the case for this sample based on a comparison o f the results to the results on the other three runs. The 4,4

- MDI result was in fact highest during the first run, which also may explain why this is the only sample with detectable concentrations on the filter. In terms of f low variability

, five of the sa mples had 10

- 20% chan ge in flow during the sampling. A comparison of the results for these samples to the results for samples that had less than 10% flow variability issues indicates that the samples with higher flow variability do not appear biased in
any one direction, and we do not believe flow variability affected the results

.

For the amines

, no br eakthrough was observed on the tubes, and the flow variability was low ( all varied less than 6 %). No amines were detected on two field blank s and a lab blank

. The only issue observed was one post

- spray area sample during the fourth run showed a concentration of PMDTA on the back section of the tube but none on the front. Most likely, this sample was attached backwards during the sampling event. Since no P MDTA were found on the front section, we believe the back section was sufficient to capture the PMDTA present in the air and this can be considered a valid sample.

For the fire retardant, TCPP was not detected on two field blanks or the lab blank , and no flow

v ariability in excess of 8 % was noted , with one exception, and no breakthrough in excess of 3% was noted , with one exception

. The exception was the area sample collected during spraying for the third run, which showed 23% flow variability and excess b reakthrough at 17% . The varying flow rate may have resulted in the breakthrough, and e xcess breakthrough can be an indication of potential sample loss. A compari son of the result for this sample to the area results during spraying for the other three runs indicate that this sample had the lowest concentration of TCPP, 0.02 ppm
, compared to 0.03 to 0.16 ppm during the other runs. So, the area result for the third
spray may be biased low.

For the HFC

- 134a, flow variability and breakthrough are not assesse d since a badge was used for sampling. The two field blanks did show some HFC

- 134a, with 20 and 27 μg detected. These results were not subtracted from the other sample results. A comparison of the uncorrected sample results to the sample results corrected for the field blanks indicate that the interpretation of the results would not be affected. That is, all of the HFC

- 134a results during spraying were well over the exposure limit both with and without blank correction, and all of the results post

spray wer e b e low the exposure limit both with and without blank correction.SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 6 of 12 Fax: 610.438.8307 

### Air Sampling Results
Tables 5 through 8 show the results of our industrial hygiene air sampling. A discussion of the results for eac h analyte follows

.

MDI

As shown in Table 5

, the applicator’s exposure and all of the area samples for 4,4

- MDI were below the exposure limit

. The applicator results during spraying were 0.0005 to 0.001 ppm for 2,4

- MDI and 0.0012 to 0. 004 ppm for 4,4

- MDI . The area sample concentrations for 2,4

- MD I and 4,4

- MDI during spraying were as high as 0.0009 and 0.0014 ppm, respectively. The area results were consistently lower than the applicator’s exposure results. pMDI was not detected for the applicator or in the area samples during spraying. The three MDI analyt es (2,4

- MDI, 4

- 4

- MDI, and pMDI) were not detect ed during the four post

- spray sampling period s. L imits of detection d uring the post

- spray period were 0.04 to 0. 05 mg/m3 for pMDI and 0.00015 to 0.00016 ppm for 2,4

- MDI and 4

- 4

- MDI.

C atalyst (Amines)

As shown in Ta ble 6

, the applicator’s exposure s and area concentrations for PMDTA during spraying were 1.01 to 3.77 ppm. T he area samples were generally higher than the applicator samples during spraying , on 3 of 4 runs

. PMDTA was detected during the post

- spray sampling period for all four runs . The post

- spray concentration during the first run was 0.5 ppm, compared to post

- spray concentrations between 0.07 to 0.11 ppm for the second through fourth runs. The first spray result was likely higher due to the fact that only B side was sprayed for one

- half of one insert, leading to a relatively large amount of unreacted catalyst left in the room after spraying.

Fire Retardant (TCPP)

As shown in Table 7

, during spraying TCPP concentrations were 0.04 to 0.22 ppm for the applicator and 0.02 to 0.16 ppm for the area sample. The 0.02 ppm area sample result may have been biased low due to sample breakthrough. During the post

- spray sampling period

, TCPP concentrations were 0.002 to 0.0034 ppm.
Blowing agent ( HFC

- 134 a)

As shown in Table 8, the concentrations for HFC

- 134a were over its exposure limit during spraying . The applicator exposures ranged from approximately 5,000 to 11,000 ppm and t he area samples during spraying ranged from approximately 6,000 to 8,000 ppm , compared to theSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 7 of 12 Fax: 610.438.8307 expo sure limit of 1,000 ppm . During the post

- spray sampling period, all of the samples were below the exposure limit, between 188 to 590 ppm.



### Conc l u sions

The concentrations of HFC

- 134a were well over its exposure limits during the application of spray polyurethane foam for 15 minutes in a chamber with 10 air changes per hour. The concentrations of 4,4

- MDI, however, were below its exposure limit during the application. T he concentration s of both HFC

- 134a a nd 4,4

- MDI were below their exposure limit s during the post

spray sampling period (30 to 90 minutes after spraying) for all four runs. 

### Revision History

2/8/2013

– Quantitation limits (also referred to herein as detection) for pMDI revised, and HFC

134a t able revised with detected blank concentrations.



### Key to Tables

The following is a key to abbreviations and notes on the tables.

*= flow variation between pre

- and post

- calibration was between 10

- 20% **= flow variation between pre

- and post

- calibration was 23 % +=breakthrough to back section or filter was 17

- 18%

^ = tube may have been backwards during sampling, but data appear valid mg/ m3 = milligrams per cubic meter ppm = parts per million
L = Liters
min = minutes ug = micrograms Lpm = Liters per minute
OEL = Occupational Exposure Limit OSHA PEL = Occupational Safety and Health Administration Permissible Exposure Limit ACGIH TLV = American Conference of Governmental Industrial Hygienists Threshold Limit Values AIHA WEEL = American Industrial H ygiene Association Workplace Environmental Exposure Levels TWA = time weighted average, adjusted to eight hours STEL = short term exposure limit, over 15 minutes ach = air changes per hour n/a = not applicableSABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 8 of 12 Fax: 610.438.8307 Table 5

. MDI Results, Low Pre ssure (2 Component) SPF Kit For mulation, 10 ach, September 10

- 11, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 9 of 12 Fax: 610.438.8307 Table 6

. Amine Results, Low Pressure (2 Component) SPF Kit Formulation, 10 ach, September 10

- 11, 2012

Table 7

. TCPP Results, Low Pre ssure (2 Component) SPF Kit For mulation, 10 ach, September 10

- 11, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 10 of 12 Fax: 610.438.8307 Table 8

. HFC

- 134a Results, Low Pre ssure (2 Component) SPF Kit For mulation, 10 ach, September 10

- 11, 2012SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 11 of 12 Fax: 610.438.8307 

### APPENDIX A SAMPLING METHODS

This section describes the methods used to monitor for the chemicals during SPF application. For more detail, please see the May 2011 ACC CPI research proposal.

SKC Aircheck 52 (Model 224

- 52), SKC AirLite , and Buck Libra pumps were used for active sampling. The calibration of e ach pump was verified using a primary flow standard

. The samples were analyzed by the laboratories and methods shown in Table A1

.

Table A1 : Air Sampling and Analytical Methodology for Select SPF Constituents.

CAS # Analyte Analytical Laboratory
and Method Flow
Rate Sampling media and limit of
detection.

101

- 68

- 8 Methylene bisphenyl isocyanate

(MDI) Bayer; HPLC with UV Detection; BMS IH Laboratory Method
Nos: 1.20.0 and 1.7.7 1.0 Lpm Midget impinger with 15 mL toluene / 1

- (2

- pyridyl) piperazine, followed by: 13 mm glass fiber fil ter treated with 1

- (2

- pyridyl) piperazine and diethyl phthala te housed in a Swinnex cassette, field extracted with 90/10 (v/v) acetonitrile/dimethylsulfoxide 9016

- 87

- 9 Polymeric MDI (pMDI)

(3

- ring and larger oligomers of MDI)

811

- 97

- 2 1,1,1,2

- Tetrafluoroethane (HFC

-

134a) Assay Technology; Modified OSHA 7 N/A Diffusive sampler

– Assay Technology Sampler No.548

13674

- 84

- 5 Tris

- (1

- chloro

- 2

- propyl) phosphate

(TCPP) Bureau Veritas; GC/NPD ICL

- IP Method No GC 024

- 1 1.0 Lpm XAD

- 2 tubes; SKC 226

- 30

- 16

3030

- 47

- 5 Pentamethyldiethylenetriamine

(PMDTA) Bayer; Bayer Method No. 2.10.3, desorption with acetone and analyzed by GC/NPD 0.50 Lpm XAD

- 2 tubes; SKC 226

- 30

- 06SABRE Health & Safety www.sabresafety.net

1015 Zucksville Road Phone: 866.734.0127 Easton, PA 18040 Page 12 of 12 Fax: 610.438.8307 

### APPENDIX B PHOTOGRAPH

Figure B1. SPF Application Sampling Locations