# 350983 OPPT-2011-0182 63130000019 p. 27



### HUMAN HEALTH RISKASSESSMENT OF VOLATILE ORGANIC COMPOUND EMISSIONS FROM A SPRAY-APPLIED 

### POLYURETHANE THERMAL INSULATION

Submitted to: Brad Boyle, A

.Sc.T. Saskatchewan Research Council Building Performance Unit Alternative Energy and Manufacturing Division Saskatchewan Research Council 15 Innovation Boulevard Saskatoon, Saskatchewan S7N 2X8

Prepared by: Dr . Lalita Bharadwaj Toxicologist College of Nursing 107 Wiggins Road University of Saskatchewan Saskatoon, Saskatchewan S7N 5E5 Email : Ialita.bharadwaiCa?usask .ca

Phone: 966-1490 W n W O --~ rTl N

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# COMPANY SANITIZEDHealth Human Risk Assessment

TABLE OF CONTENTS

. . EXECUTIVE SUMMARY .. ... . ... ... .... ... .. . .. . .. . ... . ... . ... .. . ... .... ... . .. .... .. ... . ... . ... ... . ... . ... . .. .. ... . . . .. . .. . ... . ... . ... . .. .... ... . . . . . . . . . .u 1 .0 INTRODUCTION.. ... . .. .... .... .. . .. . .. . .. . ... . ... . .. .. . . ... .... ... . .. .... .. ... . ... . ... . . .. ... . ... . ... . .... . . .. .... ... . ... . ... . ... ... ... . . . . . . . . . . 1 2.0 RISK ASSESSMENT .. .... .... ... .. . ... . . . ... . ... . ... . . . ... .... ... . .. .... .. . .. . ... . ... . .. .. . .. ... . ... . .... . . . .. . .. . .. . ... . ... . ... . .. .... . . . . . . . . .9 3.0 HAZARD INFORMATION .. . . . ... . . . ... . ... . ... . .. ... .... .... .. .... .. . .. . ... . ... . .. .. .. . ... . ... . ... . . . . ... .. ... . ... . ... . ... . ... ... . . . . . . .1 I 3.1 Selection of Contaminants of Potential Concern. ... . .. . .. . .... ... .. ... . ... . . . . ... .. .... ... . ... . ... . ... . .. . . . . . . .11 3.2 Hazard Information .. . . . ... . . . ... . ... . ... . .. . .. . ... ... . .. . .. . .. . .. . ... . .. . ... .... . ... .. .. . ... . . . . ... .. . .. . .... ... . ... . ... . .. . . . . . . .15 3.2 .1 Pentamethyldipropylenetriamine . . ... .. .. . . ... . ... ... .. .. .. .. .. .. . ... . . . . ... .. .. .. . ... . .. . ... . ... . ... . . . . . .16 4.0 DOSE RESPONSE ASSESSMENT .. .. .. . ... . .. .. .. . .. .... ... ... .. . .. . ... . ... . .. .. .. . ... . ... . .... . . . . .. ... . ... ... .. . . ... . ... . ... . . . . . .23 4.1 Threshold LimitValues and Dose Response Assessment. .. .. . .. .. ... . . . . ... .... ... . ... .. ... . . ... . ... . . . . . . 23 5.0 EXPOSURE ASSESSMENT .. .. ... . .. .. .. ... . ... . ... . .. ... . ... .. . ... ... . . . ... . ... . .. .. .. .. .. .. .. . .... . . . . .. . ... .... .... ... . . . .... ... . . . . . .25 6 .0 RISK CHARACTERIZATION . .. . ... .. . ... . ... . ... . . . ... .... .. .. .. ... . . . ... . ... . ... . .. .. ... . .. . .... . . .. .. .. .. .... .... .... .. . ... . .. . . . . . . 26 7.0 RECOMMENDATIONS. .. .. .... .. . .. . ... . .. . .. . ... . ... . . ... . . ... ... ... ... . . . ... . ... . ... . ... . ... . .. .. .. .. . .. ... . .. .... .... .... ... . . . ... . . . . . .29 8 .0 CLOSURE . .. ... . ... . ... .... .... ... . .. .... .. . .. . ... . .. . ... ... . ... . .. .. . . ... ... ... ... . . . ... . ... . ... . ... . ... . .. . .... . . .. .... .. .... .... .... ... . .. . .. . . . . . .30 9 .0 REFERENCES... .. .. . ... .... ... . .. .... ... .. . ... . .. .. .. . .. . ... . .. . .. . ... ... ... ... . . . ... . ... . ... . ... . ... . ... .... . . . . .... .. . ... .... .... .... ... . . . . . . . .31 TABLES

: Table 1 : Maximum

Measured Concentrations VOCEmissions and Time of Detection... .. .. ... . .. . ... .... .... .. . . . . . . . 7 Table 2: Maximum

Measured Concentrations and Threshold Limit Values . . ... . .. .. ... . . . . . ... .... ... . .. . ... . ... .... .. . . . . . 12

Lalita Bharadwaj, Ph.D. i November 10, 2009Health Human Risk Assessment EXECUTIVE SUMMARY Lalita Bharadwaj, Ph.D. undertook a Human Health Risk Assessment for a spray-applied polyurethane thermal insulation sample identified as and developed by Demilec Incorporated. The Saskatchewan Research Council performed emissions testing of in accordance with the Underwriters Laboratories of Canada, CAN/ULC-S774-09 Testing Standard . Headspace and dynamic chamber analyses were performed on test specimens of the thermal insulation and volatile organic compound (VOC) emissions were characterized by gas chromatography-mass spectroscopy. The purpose of the risk assessment was two-fold: 1) to determine whether volatile organic compound (VOC) emissions from , pose a health risk to individuals residing in homes or buildings insulated with this product and 2) to determine an acceptable residential occupancy time for The health risk assessment was undertaken using guidelines, protocols and methodologies proposed and readily accepted by Health Canada and the Canadian Construction Materials Centre. These guiding principles of risk assessment were utilized to predict the human health risk associated with potential exposure to VOCemissions from Careful consideration of all relevant chemical and toxicity data was given to the assessment to determine the potential for health risk. The assessment accounted for the potential for human exposure to maximum indoor air concentrations of each VOC emission product identified through dynamic chamber analysis of the polyurethane formulation. The assessment took into consideration the chemical nature and toxicity information of the VOC emissions, potential for human exposures, the magnitude, frequency and duration of human exposure to each VOC product, and their individual decay patterns over a 30-day period of dynamic chamber analysis. The assessment also included comparisons (including stringent safety margins) between potential exposure to maximum

possible levels and the toxicological profiles of the VOCproducts emitted.

Lalita Bharadwaj, Ph .D. ii November 10, 2009Health Human Risk Assessment The conclusion oj'this assessrnenl is that prray-applied polyurelhane thermal insulation product developed by loes not pose a health risk to individuals residing in homes or buildings insulated with this material . Based on the decay pattern of the VOC products (up to 30 days), the concentration of individual airborne VOC and/or total VOC (TVOC) decrease very rapidly over time. In general, maximum

airborne emission concentrations of VOCemission products measured within 1 hour of dynamic chamber analysis were found to be well belowthe safety guidelines applied in the process of this risk assessment . Considering that VOC emission products were classified as having a low order inhalational toxicity following short and/or long term low-level exposures and the maximumemission concentrations were belowthe safety standards applied in this risk assessment, it was concluded that airborne concentrations of VOC or TVOC emitted from would be considered safe for human exposure. Emission concentrations, within 2 hours after the application of ', will not pose a significant human health risk to individuals residing in homes insulated with this material . Overall data suggest a lowrisk for adverse inhalational exposures and a low potential for health risk. Ambient indoor air concentrations at 2 hours after application will be well within an acceptable range for human exposure. Therefore, the recommended limiting residential occupancy time for is 2 hours and applies to residents ofstructures insulated with this material .

Lalita Bharadwaj, Ph .D. November ]0, 2009Health Human Risk Assessment 1 .0 INTRODUCTION In October 2009, Dr. Lalita Bharadwaj undertook a human health risk assessment to evaluate the potential impacts on human health from exposure to Volatile Organic Compound (VOC) products emitted froma spray-applied polyurethane thermal insulation

Volatile organic compounds are chemicals that contain carbon and hydrogen. Typically, VOC have high vapour pressures, easily vaporize at normal temperature and pressure and have boiling points that range from 50-250°C. Several thousand compounds both natural and synthetic are classified as VOC . These include carbon-based molecules, such as aldehydes, ketones, alcohols, amines and hydrocarbons. Many of these volatile organic compounds are ubiquitously present, at lowlevels in various indoor air environments (office, home and workplaces) . Standard approaches of risk assessment were utilized to characterize the human health risks associated with potential exposures to VOC emitted from the spray-applied polyurethane product. In this case the risk assessment was based on maximumlikely exposures to VOCemission products. It was assumed that individuals would be exposed acutely (short-term) and/or chronically (long-term) to maximum concentrations of VOC emission products as determined by dynamic chamber analysis Polyurethane foam is commonly utilized in a variety of applications; for example furniture cushions, shoe soles, insulating materials, adhesives, flotation devices, cellular scaffolding for bone regeneration, and acoustical vibration control . Polyurethane (PU) spray foams are thermal insulating products and are commonly used in commercial, institutional and residential construction . Currently, there is an incomplete source of toxicity data evaluating the potential human health effects associated with exposures to PU spray foam or to its volatile organic compound (VOC) emission products under conditions other than those associated with occupational exposures. The potential short or long-term health effects associated with exposure to this material in the general Lalita Bharadwaj, Ph.D. 1 November 10, 2009Health Human Risk Assessment population are fundamentally unknown. Due to the lack of detailed toxicity information, the human health risks associated with short and/or long-term exposures to PU spray foams and their emission products can only be predicted by the application of human health risk assessment protocols (1,2) . Spray-applied PU foam insulation products manufactured and developed for use in residential or commercial buildings must undergo standardized VOC emissions testing before commercialization and approval by the Canadian Construction Materials Centre (3) . For polyurethane formulations intended for use in residential spaces, VOCemissions are to be tested in accordance with appropriate methods outlined in the Underwriters Laboratories of Canada, CAN/ULC-S774-09 ; Standard Laboratory Guide for the Determination of Volatile Organic Compound Emissions from Polyurethane Foam . These include both Headspace (HS) and dynamic chamber analysis (DCA [Procedure B]) methods described herein. Headspace analysis involves an initial screening of VOC emissions fromatest specimen of a polyurethane product that has aged for approximately 20to 24 hours. Procedure B of the Underwriters Laboratories of Canada dynamic chamber analysis, determines polyurethane VOC emission profiles over a 30-day period of testing. In general, DCA is a procedure used to identify, quantify, and determine emission rates of VOC(s) released fromcommercial formulations of PU spray foam insulation. The results obtained by dynamic chamber analysis of PU foamproducts are used to predict potential indoor air concentrations of VOC emission products that could occur in a typical residential or workplace building insulated with PU. These data provide a quantitative estimate of the potential levels of human exposure to PU-derived VOCemission products and are vital for determining the degree of human health risk associated with exposure to these chemicals in the household, workplace or other inhabited structures. Headspace and dynamic chamber analyses were performed to characterize VOC emissions `he spray-applied PU thermal insulation developed by walysis was completed by Brad Boyle, A .Sc.T, Technologist of Lalita Bharadwaj, Ph.D. 2 November 10, 2009Health Human Risk Assessment the Saskatchewan Research Council, Saskatoon, Saskatchewan ; using procedures outlined in CAN/UCL-S774-09 [Standard Laboratory Guide for the Determination of Volatile Organic Compound Emissions from Polyurethane Foam] (4) . Head Space analysis was performed on a sample of hat was aged for 24 hours. Using CarbotrapTM400 absorbent tubes, in conjunction with gas chromatography-mass selective detector analysis; the number, chemical nature and the relative concentrations of VOCproducts emitted fromthe insulation material was determined . Headspace analysis revealed that 5 VOC products; pentafluoropropane, dichloropropane, methyldioxane, dimethyldioxane and trimethyldioxolane, were emitted from the test specimen. The relative airborne concentrations of the emitted VOC products, from the specimen tested ranged in concentration from0 .019 Mg/M3 to 0

.180mg/m3

. The emission products were chemically classified as halogenated, aliphatic and aromatic hydrocarbons and emissions levels were considered very low . Subsequent to headspace analyses, discrete dynamic chamber analysis was performed on the insulation product (4) . Dynamic chamber analysis determined the VOCemission profiles of the polyurethane product for a 30-day period . VOC emission products were measured in air samples taken at specified time intervals (1, 12, 24, 48 hours and 4, 7, 14, and 30 days), as prescribed by the CAN/UCL-S7774-03 Standard. A re-test at the I- hour interval of DCA was also performed on the test specimen. The 1- hour retest was preformed due to the discovery of an open valve (refer to SRC report) 42 minutes after the initiation of the DCA . The identification and airborne emission concentrations measured at the 1-hour pretest were slightly different than those detected in the initial 42 minutes of DCA . However, airborne concentrations detected in air samples collected at both sampling periods were low (4) . Airborne VOC emissions ranged in concentration from 0 .035 Mg/M3 to 0

.433 Mg/M3 and 0

.010 Mg/M3 to 0

.084 Mg/M3 in the initial 45 minutes and the 1-hour retest respectively. A table of confidence of VOC identification was summarized in the SRC report (4) and in general indicated good confidence of identification for the VOCdetected.

Lalita Bbaradwaj, MD . 3 November 10, 2009Health Human Risk Assessment The results obtained by dynamic chamber analysis are summarized belowand were utilized as a quantitative estimate of the potential levels of human exposure to

-derived VOC emission products. These data were applied to the risk assessment process to determine the degree of human health risk associated with the potential exposure to these specific VOC emissions from the

product. A total of 13 VOC emission products were identified through DCA analysis of

(4) . The VOC emission products were as follows: 1) Pentafluoropropane, 2) Dichloropropane, 3) Methyldioxane, 4) Dimethyldioxane, 5) Trimethyldioxolane, 6) Chlorobenzene, 7) Propane oxybis (chloro), 8) Dimethyoxy propane, 9) Trimethylpropanoic acid, 10) Methylbenzene, 11) Phenoxyethanol, 12) Methylpropanamine and 13) Pentamethyldipropylenetriamine . Not one air sample collected for DCAcontained all 13 VOCemissions . Ten VOC emission products were measured in air samples collected in the initial 42- minute period of DCA testing. With the exception of 3 VOC (dichloropropane, trimethylpropanoic acid and phenoxyethanol) products, the VOCemissions profile identified at the 1-hour retest were similar in nature to the emissions profile identified in samples collected in the initial 42- minutes oftesting. A total of 9 VOC products were measured in air samples collected during the 1 hour DCA retest and emission concentrations were found to be less than those measured in the initial 42-minutes oftesting. Two VOC products (pentafluoropropane and pentamethyldipropylenetriamine) were measure at the 12-hour DCA testing interval and one of these emission products was not previously identified in air samples collected for analysis. One previously unidentified Lalita Bharadwaj, Ph .D. 4 November 10, 2009Health Human Risk Assessment VOC product (pentamethyldipropylenetriamirne) was detected at concentrations of 3.21 mg/m3 in air samples collected for analysis at the 24-hour testing interval . With the exception of pentafluoropropane, methylpropanamine and pentamethyldipropylenetriamine, VOC emissions fell to undetectable within 12 hours of DCA testing. Pentafluoropropane was detected, at lowlevels (0.019 mg/m3 to 0 .062 mg/m3), in air samples collected at l, 12 and 24 hours of DCA . The maximum

emission concentration of 0

.062 mg pentafluoropropane /m3 was identified at the 12 hour testing interval . Methylpropanamine, at a concentration of 0 .067 mg/m3, was only detected in air samples collected at 12 hours of DCA . Pentamethyldipropylenetriamine, at a concentration of 3.21 mg/m3 was only detected in air samples collected at the 24 hour DCAtesting interval . With the exception of 4 VOC emission products (pentafluoropropane, phenoxyethanol, methylpropanamine and pentamthyldipropylenetriamine) maximum VOC emission concentrations were detected in air samples collected within the initial 42 minutes of DCA. With the exception of pentafluoropropane, phenoxyethanol, methylpropanamine and pentamethyldipropylenetriamine, emission concentrations identified for each VOC subsequent to the initial testing period (42-minutes) were detected at levels well below their respective maximum emission concentrations . Overall, the maximumairborne VOC concentrations emitted from were generally identified in air samples collected at the initial 42-minute period of DCA testing. Airborne VOCconcentrations measured in air samples collected in the initial 42- minutes of sampling ranged in concentration from 0 .035 to 0

.433 mg/m3

. Generally, measured airborne VOC concentrations collected subsequent to the initial 42-minute period of analysis, ranged in concentration from undetectable to well below their maximummeasured airborne concentrations. A reviewof the DCAanalyses indicate that erived VOCproducts are emitted at low-levels and do not persist in air samples collected over the 30 day duration Lalita Bharadwaj, Ph.D. 5 November 10, 2009Health Human Risk Assessment of DCA testing. The nature and total number of VOC emission products identified fluctuate from 10 to 9 to 2 over a 24-hour period. With the exception of 2 VOCproducts emissions drop to undetectable within 12-hours of DCA . In general, the magnitude of VOCemissions drop rapidly over the 30-day testing period from the maximum emission levels, generally defected at 42-minutes, to undetectable within 12 hours of DCA testing. Based on the air sampling data it is evident that the nature and total number of VOC products emitted from fluctuate overtime. In general the emission concentrations ofeach VOCproduct decrease to zero within 12 hours and the emissions are transient and not maintained over the 30-day period ofDCA testing

. The maximumindoor air concentrations of each VOCemission product and the time in which these levels were detected through DCA of ` 4) are summarized in Table 1 . The maximummeasured airborne concentrations of the 13 VOC compounds identified were measured within 42-minutes of DCA testing. Maximum emissions concentrations of phenoxyethanol were detected in air samples collected at the 1 hour retest . Maximum

emission concentrations of pentafluoropropane and methylpropanamine were detected in air samples collected at 12 hours of DCA. Maximum emission concentrations of pentamethyldipropylenetriamine were detected in air samples collected at 24 hours of DCA

.

Lalita Bharadwaj, Ph .D. 6 November 10, 2009Health Human Risk Assessment

Table 1 : MaximumIndoor Air Concentrations of VOCEmission Products

from id Time of Detection. VOC_Emission Product Identified MaximumIndoor Air Concentration m

7m3 Time of Detection

minutes 1,1,1,3,3-Pentafluoropropane 0.062 12 hour Dichloro ro ane 0 .115 42 Meth Idioxane 0 .032 42 Dimeth ldioxane 0 .431 42 Trimeth ldioxolane 0 .237 42 

### Chlorobenzene 0.150 42 Propane ox bis chloro 0.056 42 Dimethox ro ane 0.035 42 Trimeth I ro anoic acid 0 .433 42 Meth lbenzene 0 .053 42 Phenox ethanol 0 .025 1 -our retest Meth 1 ro anamine 0 .067 12 hour Pentaemthyldipropylenetriamine 3.21 ~ 24 hour In summary, review of the DCA data for indicate that peak concentrations of VOC emission products would likely be reached within 42-minutes of application to a residential building. The total number of volatile organic compounds emitted from to ambient air would fluctuate from 10 to 9 to 2 during a 24 hour testing period (refer to SRCreport [4]) . Maximum airborne concentrations drop over the testing period suggesting these levels would not be maintained in a residence for extended periods. In general, DCA indicates that airborne concentrations of VOC decrease over time to concentrations significantly lower than the maximum measured peak concentrations and ultimately fall to undetectable levels within 12 hours of testing. Overall, dynamic chamber analysis reveals that VOCproducts from are initially emitted at lowlevels and would ultimatelyfall to undetectable levels within 24 hours after its application. The maximumindoor air concentrations, summarized above in Table 1, represent the highest estimated level of human exposure to VOC products emitted from Lalita Bharadwaj, Ph.D. 7 November 10, 2009Health Human Risk Assessment "Sealection 500" The time in which maximumVOC concentrations were detected specifies the point in time when maximumconcentrations would be reached in a residence following the application of this PU foam insulation (ie. it is assumed that individuals occupying homes 42-minutes and, in the case of phenoxyethanol, pentafluoropropane, methylpropanamine and pentamethyldipropylenetriamine, I hour, 12, and 24 hours after the application of the PU foam insulation to their residence would be exposed to these levels) . The maximum measured concentrations of each VOC emission product along with its time of detection were utilized in the process of a human health risk assessment to evaluate the potential human health risk that may be associated with the exposure to maximum

airborne VOCemissions derived from The toxicity of each VOCemission product was addressed in the assessment . The human health risk assessment was conducted using conservative assumptions that would lead to an overestimation of potential exposure and risk. Thus in this case, a "worst case scenario" was applied to the assessment . In this scenario it was assumed that human exposure levels that would occur in a typical residence are equal to the maximum measured air concentrations detected by DCA of Although, DCA reveal that maximum levels are not maintained in air for extended periods, the assumption that human exposures are equal to maximum measured airborne concentrations provides an ample margin of safety to assess risk to human health. These assumptions were utilized in the assessment of human health risk and the following questions were addressed in this particular risk assessment process. 1) Will exposure to maximum indoor air concentrations of VOC emission products from ;outlined in Table 1) pose a significant human health risk to residents of homes or buildings insulated with this construction material? 2) What is the limiting residential occupancy time for ' ? (ie. When is it safe for individuals to reside or enter buildings following the application ofthe

Lalita Bharadwaj, Ph.D. 8 November 10, 2009Health Human Risk Assessment 2.0 RISK ASSESSMENT Risk assessment is a process that involves the characterization of the probability of adverse human health effects that may be associated with exposure to environmental chemicals (1,2,5) . This process was used here to predict the potential for human health risk associated with short and/or long-termexposure to VOC products emitted from the polyurethane product he risk assessment process is divided into four major steps; hazard identification, dose-response assessment, exposure assessment and risk characterization and are briefly outlined below . The first step, hazard identification, involved the identification of Contaminants of Potential Concern (COPC) . In this step of the risk assessment, VOCemission products were evaluated for their safety through reviewof available toxicity data. The maximum measured concentrations of each VOC emission product were compared to levels of exposure that have been accepted as "safe" for industrial workers. Accepted levels of exposure signify Threshold Limit Values (TLV) and/or Occupational Exposure Limits (OEL) . These values of exposure are assigned by governing occupational agencies such as the American Conference of Industrial Hygienists [ACGIH] (6), National Institute for Occupational Safety and Health [NIOSH] (7) and the Occupational Safety and Health Administration [OSHA] (8) . However there are cases where TLV values have not yet been assigned to chemicals or VOC emission products. Thus in this case, maximum indoor air concentrations of VOC emission products were compared to a no observed adverse effect level (NOAEL) derived from animal/human toxicity data (1,2,5) and/or a TLV value assigned to a compound similar in chemical nature to the identified VOC product. In addition to the identification of COPC, the first step of the risk assessment process involved the review of pertinent toxicity data (which may include inhalational, reproductive, developmental, carcinogenic, mutagenic and/or genotoxic information), chemical characteristics and occupational exposure limits for each COPC when and if available. Lalita Bharadwaj, Ph.D. 9 November 10, 2009Health Human Risk Assessinent

In the second step of the risk assessment process the dose-response relationship was evaluated for the COPC identified. Generally, adverse health effects will only occur when an agent is absorbed by the human receptor and distributed to target organs/tissues at concentrations and for durations of exposure sufficient to elicit toxicity. Therefore the nature of the relationship between the received dose and the probability of an adverse biological response was evaluated in the dose-response step of the risk assessment . In this step the relationship between the magnitude of the received dose and the occurrence of an adverse health response was characterized (1,2,5) . The dose-response assessment considers whether exposure to maximum measured concentrations of airborne COPC would result in an absorbed dose posing a potential human health risk. The third step in the risk assessment process involved defining the type of human exposure to VOC emission products identified as COPC . This step included [1] describing the magnitude, frequency and duration of exposure to VOC(s) emissions and [2] identifying the possible exposure routes. In the case of emission products from the

] the magnitude, frequency and duration of exposure was classified as continuous low-level and [2] the main route of exposure was via the respiratory tract. The potential for human health risk is characterized in the fourth and final step of the risk assessment process. The likelihood that humans may experience toxicological effects under the actual conditions of exposure was determined here. In this case, it was determined whether individuals are at risk of experiencing adverse health effects by residing in buildings insulated with the PU foam insulation manufactured by

Lalita Bharadwaj, Ph.D. 10 November 10, 2009Health Human Risk Assessment 3.0 HAZARD IDENTIFICATION This section summarizes the contaminants of potential concern that were selected for this assessment . A reviewof DCA of indicated that there were 13 VOC emitted fromthe polyurethane foam insulation product. The VOCemitted were primarily classified as aliphatic and aromatic hydrocarbons. The maximum measured concentrations of each VOCemitted as identified through DCA of were summarized above in Table 1 . 

### 3.1 Selection of Contaminants of Potential Concern (COPC) Based on human health considerations, a selection process was performed to identify contaminants of potential concern (COPC) fromthe list of VOC products emitted from

The procedure followed for selection of COPC for human health is described below

. Firstly, contaminants of potential concern were identified by comparing maximum measured concentrations of each VOCto 1 % ofthe American Conference of Government Industrial Hygienists (ACGIH) 2004 Threshold limit values established for these chemicals. The ACGIH TLV-TWA divided by 100 is industry protocol for establishing chronic human exposure levels suitable for residential scenarios (24 hours per day, 7 days per week) . Maximum measured concentrations of VOC emission products at concentrations exceeding the above referenced guideline were considered COPC . In other words, these VOCemission products were considered to demonstrate a potential to cause adverse health outcomes under prolonged or repeated exposure. Table 2, summarizes the VOCemission products identified as COPC, their maximummeasured concentrations and their respective ACGIHTLV-TWA values divided by 100 .

Lalita Bharadwaj, Ph.D. 11 November 10, 2009Health Human Risk Assessment Table 2: MaximumIndoor Air Concentrations of VOCEmission Products from and ACGIHTLV-TWA (regulatory limit) =100 . VOCEmission Product Identified MaximumIndoor Air Concentration (mg/m) 

### MOM 3) 1,1,1,3,3-Pentafluoro rp opane Dichlorooronane Methvldioxane Dimethvldioxane Trimethvldioxolane Chlorobenzene Prooane oxvbis (chloro Methvlbenzene Phenoxvethanol Methvlvropanamine Note : 0 .062 0 .115 

### 0.032 0 .431 0 .237 0 .150 0 .056 

### 0.035 ACGIHTLV-TWA

(regulatory limit) =100



### - Il' ` 3 3. -- - ;- 0 .053 0 .025 0 .067 841 .730 0 .462 00.720 00.720 e0.606 0 .460 0 .210 

### '3.69 0 .754 7.40 °0.120

aAn exposure limit of 1,000 ppmor 4173 mg/m3 (8-hour time-weighted average) was recommended by the American Industrial Hy.-icne Association, Workplace Environmental Exposure Limit (WEEL) Committee. bACGIH TLV-TWAfor 1,4-Dioxane `ACGIH TLV-TWAfor Propionic Acid dACGIH TLV-TWA for Methylamine `ACGIH TLV-TWA for Dioxolane fBased on the toxicity and chemical nature of his (2-chloroisopropyl) ether a workplace environmental exposure level (WEEL) : 8-hr Time-weighted Average (TWA) of 3 ppm (21 mg/m3) (52) . The TWA of 21 mg/m' will be utilized in this risk assessment to evaluate the potential for human health risk associated with exposure to propane, oxybis (chloro) . $ACGIH TLV-TWA for Diethylenetriamine hOSHA Standards:Ethylene glycol monophenyl ether Permissible Exposure Limit: TableZ-1 8-hr TimeWeighted Avg: 200 ppm (740 mg/cu m) . Skin designation .[29 CFR 1910.1000 ; U .S. National Archives and Records Administration's Electronic Code of Federal Regulations. Available from, as ofFebruary 10, 2004: http://www

.gpoaccess.gov/ecfr] 'ACGIH TLV-TWAfor propyleneglycol monomethyl ether 'ACGIH TLV-TWAfor Diethylenetriamine As summarized in Table 2, the 13 VOCemission products emitted from' have available ACGIH TLV-TWA for comparative purposes. The maximummeasured concentrations identified for 11 VOC emission products [pentafluoropropane, dichloropropane, methyldioxane, dimethyldioxane, trimethyldioxolane, chlorobenzene, propane oxybis (chloro), dimethoxypropane, methylbenzene, phenoxyethanol and methylpropaneamine] were found well below their respective ACGIH TLV-TWA Lalita Bharadwaj, Ph .D. 12 November 10, 2009Health Human Risk Assessment divided by 100

. The CCMC considers that I% (0.01) of the TLV-TWA® value, established for a single volatile organic compound, is a permissible concentration ill indoor air and applies to possible volatile organic emissions from spray-applied polyurethane cellular plastic thermal insulation (3) . Thus in this case, a safe level of exposure was considered as TLV-TWA® = 100 . A safety factor of 100 provides an ample margin of safety and could be applied to the TLV-TWA® in this case. It was assumed here that a short-termand/or chronic lifetime exposure to levels of TLV-TWA® = 100 would not pose a significant health risk to occupants of a home insulated with

Based on the industry protocol for establishing chronic human exposure levels suitable for residential scenarios by application of a safety factor of 100 to the ACGIH TLVTWA®, the maximum emission concentrations of pentafluoropropane, dichloropropane, methyldioxane, dhnethyldioxane, trimethyldioxolane, chlorobenzene, propane oxybis (chloro), dimethoxypropane, methylbenzene, phenoxyethanol and methylpropaneamine are considered safe. Thus, the above VOC emission products were not considered as COPCand were not considered further in the risk assessment process. As detailed in Table 2, the maximumemission concentrations of two VOC products (trimethylpropanoic acid and pentamethyldipropylenetriamine) emitted from exceed the regulatory limit utilized to assess risk in this case. The maximum emission concentration of trimethylpropanoic acid was identified in air samples collected within the first 42- minutes of DCA analysis. Emissions were undetectable at all other DCA sampling intervals. Thus trimethylpropanoic acid is transiently emitted and airborne levels fall to zero within 1 hour of DCA testing. Due to the transience of this VOC emission and the unlikely event that individuals would be repeatedly exposed to high acute levels of trimethylpropanoic acid and exposed at levels that would result in adverse health effects, this emission product was not considered a COPC in this case. Thus one VOC emission product, pentamethyldipropylenetriamine, was considered a COPC and was further evaluated in the risk assessment process.

Lalita Bharadwaj, Ph .D. 13 November 10, 2009Health Human Risk Assessment As a second step in the process of hazard identification, a review of relevant toxicity data was undertaken to establish exposure limits that are considered safe and to determine the relative toxicity of the COPC identified in this case. For the purposes of this risk assessment, a reviewof the chemical and animal/human toxicity data was outlined for the VOCemission product; pentamethyldipropylenetriatnine. This information was gathered to determine if this VOC product is causally linked to any adverse health effects. The range of toxic effects attributed to an exposure to this VOCemission product is discussed in the following sections. This type of information helps to establish if short and/or longterm exposure to predicted maximum indoor air concentrations of pentamethyldipropylenetriamine would pose a significant human health risk to exposed individuals. Inhalational toxicity information was specifically addressed here since the main route of exposure was considered to be through the respiratory system . Human exposures to VOCemissions via the gastrointestinal and dermal routes of exposure were considered to be negligible in this case. Exposure levels that are considered to be acceptable ("safe") for human exposure such as the TLV-TWA®are usually allocated to various chemicals by the American Conference of Governmental Industrial Hygienists [ACGIH], however other agencies such as the National Institute for Occupational Safety and Health [NIOSH], Occupational Safety and Health Administration [OSHA] and other governing bodies of occupational and industrial hygiene assign exposure limits to chemicals. As a further step in the risk assessment process, maximum measured airborne concentrations of COPC were compared to occupational exposure limits assigned by agencies other than the ACGIH . Occupational exposure limits do not represent a fine line between safe and dangerous concentrations, nor are they a relative index of toxicity. For the purposes of this risk assessment occupational exposure limits were used to facilitate the risk assessment process and help to predict the potential for human health risk associated with an exposure to the COPC (the VOC emission products ; pentamethyldipropylenetriamine) . It is not generally recommended that occupational exposure limits be used as standards for indoor air quality in the home and for this reason the occupational exposure limits were reduced by a suitable safety factor to err on the side of caution when assessing the potential human Lalita Bharadwaj, Ph.D. 14 November 10, 2009Health Human Risk Assessment health risks associated with this particular case. The magnitude of this safety factor depends primarily on the number, the toxicity and the relative quantity of VOCemission products and other contaminants ordinarily present in the home (1,2,5,9)

. In summary, if no TLV-TWA©guidelines were established or available for the identified COPC, then maximumairborne concentrations were compared to either a TLV-TWA® -= 100 derived for a chemically similar compound, a guideline value established by another governing agency other than the ACGIH, and/or an inhalational No Observed Effect Levels = 100 [(NOEL)- an airborne concentration that produced no observed adverse effects in exposed animals] derived from animal toxicity studies. If measured concentrations were found to be belowthe NOEL = 100 value then the VOC emission product was dropped for further consideration. Only concentrations of VOC emission products that exceeded the above guidelines or derived levels (NOEL = 100; when no TLV-TWA(D guidelines were available) were selected for further consideration. The toxicity information available for the VOC emission product; pentamethyldipropylenetriamine which was considered a COPC in this case, is outlined belowin Section 3.2 under theheading Hazard Information. 3.2 Hazard Information In the present case, pentamethyldipropylenetriamine was considered a COPC . It was considered a COPC because its maximum emission concentration exceeded the exposure guideline applied in this case and summarized in Table 2 . The maximummeasured airborne concentration of pentamethyldipropylenetriamine was 3.21 mg/m3respectively. The maximum

airborne concentration of this VOCemission product was identified at the 24-hour time interval of dynamic chamber analysis. Pentamethyldipropylenetriamine was only detected in air samples collected at 24 hours of DCA . Pentamethyldipropylenetriamine was not detected in air samples collected during any other DCA testing period. Although, the maximumairborne concentration of this emission product was primarily detected at 24 hours of DCA testing and airborne levels fell to zero within the next testing period of 2 days, the worst-case scenario was assumed Lalita Bharadwaj, Ph.D. 15 November 10, 2009Health Human Risk Assessment in this case. Under these conditions, it was assumed that the rnaximum measured airborne concentrations represent human exposure levels and that individuals would be repeatedly exposed to this airborne concentration. 3.2.1 Pentamethyldipropylenetriamine The dynamic chamber analysis identified pentamethyldipropylenetriamine, an alkyl triamine, as an emission product from pray-applied polyurethane insulation. This compound was only found in air samples analyzed at the 24-hour time interval of DCA

. Maximummeasured air concentrations of 3.21 mg/m3 were detected at this time interval . Airborne concentrations dropped to zero at the next testing interval of 2 days and pentamethyldipropylenetriamine was not detected in air samples collected at time intervals prior to the 24-hour time period. These data suggest that emissions of pentamethyldipropylenetriamine are transient and would drop to zero within 2 days following the application of ' to a residential structure. Additionally, human exposures would be of an acute nature and exposures concentrations would be at lowlevels. Amines are organic compounds that contain a basic nitrogen atomand are derivatives of ammonia. One or more hydrogen atoms can be replaced by organic substituents such as alkyl or aryl groups thus giving rise to aliphatic amines. Aliphatic amines can be classified into primary, secondary and tertiary amines. Primary amines arise when one of three hydrogen atoms in ammonia is replaced by an organic substituent. Examples include; methylamine and ethanolamine. Secondary amines (dimethylamine and methylethanolamine) have two organic substituents bound to nitrogen together with one hydrogen and a tertiary amine (trimethylamine, dimethylethanolamine) has all three hydrogen atoms replaced by organic substituents . Similarily an organic compound with multiple amino groups (-NH2) is called a diamine, triamine and so forth. Pentamethyldipropylenetriamine is classified as a triamine.

Lalita Bharadwaj, Ph.D. 16 November 10, 2009Health Human Risk Assessment In a broad definition, compounds containing the structure R-NH-R' (an imine), or a diamine or triamine (containing two or three amino groups, respectively) are classified as aliphatic amines. The toxicity of most aliphatic amines may fall into lowto moderate. Such classification is based on the relatively high oral LD50 (lethal dose 50 ; the dosage required to kill 50%

of the tested animals) and inhalation LC50 (lethal concentration 50 ; the airborne concentration required to kill 50% of the tested animals) values found in rodent exposure studies (9) . The health hazard from amines arises primarily fromtheir caustic nature. All lower aliphatic amines are severe irritants to the skin, eyes and mucous membranes. Skin contact can cause burns, while direct contact with eyes can result in corneal injury and loss of sight. Aliphatic amines generally have an odor of ammonia, and their vapors can produce irritation to the mucous membranes, respiratory irritation and cough. Like ammonia, amines act as bases but are relatively weak. However, alkylation will enhance the basicity of an amine. The ACGIH has not assigned a TLV-TWA®to pentamethyldipropylenetriamine. Due to the lack of an assigned TLV-TWA® the toxicity data presently available for diethylenetriamine, an alkyl triamine which is classed as a highly corrosive alkyl triamine was utilized to asses risk to health in the process ofthis risk assessment . Diethylenetriamine is a polyamine compound, a compound that contains three amino groups. The toxicity information of diethylenetriamine was utilized in this risk assessment to evaluate potential risk associated with low-level exposure to pentamethyldipropylenetriamine emitted from' Diethylenetriamine is used in a variety of industrial applications and processes. This compound is used as a solvent, chelating agent and component of epoxy resins and curing agents. As a result of its use in many industrial applications, this triamine may enter the environment as emissions or in wastewater during its manufacture and use as a chemical intermediate however, environmental monitoring data is currently unavailable for this compound. Thus little information concerning the concentration ofdiethylenetriamine in the environmental media of air, water and/or soil and therefore, the levels of exposure to Lalita Bharadwaj, Ph.D. 17 November 10, 2009Health Human Risk Assessment this polyamine in the general population is not known. Diethylenetriamine has a relatively low vapor pressure at 25 degrees C indicating that if released to air it would exist solely as a vapor in the ambient atmosphere. Therefore exposure is primarily through the respiratory system in this case. Like other industrial emission products, vapor-phase diethylenetriamine is degraded in the atmosphere by a reaction with photochemically produced hydroxyl radicals. The half-life for diethyelenetriamine in air is estimated to be approximately 2.7 hours respectively. It is expected that in the ambient atmosphere, this chemical will react with photochemical lyproduced hydroxyl radicals and thus will not accumulate to toxic levels in a typical household or workplace environment (10) . Based on the DCA analysis of it is apparent that air borne concentrations of pentamethyldipropylenetramine are transient and fall to zero quickly. Thus it is not expected that pentamethyldipropylenetramine would accumulate to a toxic level in a residence or workplace environment, but dissipate over-time. The occupational/industrial setting is considered the primary location for the occurrence of human exposure to diethylenetriamine. Occupational exposures may occur via dermal contact and/or inhalation of vapor and aerosols at workplaces where this polyamine is produced or used (11) . The general population may be exposed to this polyamine through inhalation of contaminated ambient air, ingestion of contaminated food or water and/or through dermal contact with diethylenetriamine containing topical ointments. Exposure to diethylenetriamine would be primarily occupational via inhalation and dermal contact. Diethylenetriamine is readily absorbed through the gastrointestinal tract and 96%of the administered dose is excreted within 48 hours. Roughly equal amounts are excreted in the feces and urine with at least 4 metabolites being detected (but not identified) in the latter . Only a small proportion (<2%) is recovered as expired carbon dioxide (12) . It is likely that pentamethyldipropylenetriamine absorbtion, metabolismand excretion would be similar to diethylenetriamine suggesting that pentamethyldiprpopylenetriamine would be readily excreted from the human body following absorption into the body. Lalita Bharadwaj, Ph.D. 18 November 10, 2009Health Human Risk Assessment Skin sensitization in the general population has been observed in a few instances where individuals have been exposed to polyamines through application of polyaminecontaining pharmaceutical skin creams to occluded (damaged) skin. Skin sensitization has not been observed in industrial exposures because direct skin contact is less intimate and because damaged skin is not usually involved . Chemicals known to possess the toxicological property of skin sensitization could potentially cause allergic contact dermatitis in humans . It is therefore a possibility that dermal contact with diethylenetriamine, may have the potential to cause contact dermatitis (13) . Undiluted liquid forms of this compound are classified as corrosive agents to skin. Liquid polyamines have produced burns to human skin subsequent to a brief dermal contact (only a few minutes) with solutions of diethylenetriamine. Diethylenetriamine is characterized by its capacity to cause severe corneal injury and pulmonary and cutaneous sensitization in humans. Solutions of 15%to 100% have been reported to cause lasting corneal damage and sensitization of the skin. Vaporized diethylenetriamine has been reported to cause sensitization of the respiratory tract . In some cases it has been reported that little exposure is necessary in occupational settings to induce a high degree of cutaneous and respiratory sensitivity (14) . Dermitits and respiratory sensitivity are conditions that are usually associated with a long-termrepeated exposure to occupational levels (> 4.0 mg/m3) of triamines. The short-term emission and the relatively low emission concentration of pentamethyldipropylenetriamine is not likely to be associated with or result in skin sensitization. In general diethylenetriamine is considered a potent primary skin irritant that can cause edema and necrosis of the skin. Skin irritation is frequently complicated by a high incidence of allergic skin sensitization (dermatitis) and there is a high prevalence of skin sensitization to diethylenetriamine in workers chronically exposed (15) . Symptoms of conjunctivitis, keratitis (inflammation of the cornea), dermatitis, irritation of respiratory tract; asthmatic breathing, nause and vomiting have been reported among workers exposed to diethylenetriamine (16) . Additonally, repeated inhalation of high Lalita Bharadwaj, Ph.D. 19 November 10, 2009Health Human Risk Assessment concentrations of diethylenetraimine may result in asthmatic responses in exposed individuals (17) . Thus individuals with allergies and diseases of the skin or lungs may be more susceptible to acute high-levels of diethylenetriamine exposures. A 15%solution of diethylenetriamine has been shown to be corrosive to rabbit cornea and skin (18) . The above data indicate that both diluted and undiluted liquid forms of diethylenetriamine are likely to be corrosive to human skin following direct short-term dermal contact with this compound. Very little human and animal inhalational toxicity data is available on polyamine compounds such as diethylenetriamine. However, it has been reported that diethylenetraimine vapors of 300 ppm (1264 mg/m3) produce no adverse effects in exposed rats (19) . Although the inhalation toxicity data is limited there is some animal inhalational toxicity information on the polyamine compound, a diamine, 1,2- ethanediamine) . This information will be discussed belowand will also be utilized to assess risk to potential pentamethyldipropylenetriamine exposure from Observations of animals exposed to acute (one time exposure) high levels of 1,2- ethanediamine vapor suggest that polyamine compounds are irritants to the eyes, mucous membranes and respiratory tract under acute exposure scenarios. Inhalational exposure studies in rats repeatedly exposed to 1,2-ethanediamine vapor concentrations of 125 ppm (307 mg/m3) to 484 ppm(1190 mg/m3) for 37 hours indicate that polyamine compounds may produce lung, kidney and liver damage under these extreme conditions of exposure. The degree of organ damage increases with increasing exposure concentrations (484, 225 and 132 ppm) of 1,2-ethanediamine suggesting that exposure to increasing triamine concentrations may also result in organ damage. An exposure concentration of 125 ppm (307 mg/m3) of 1,2-ethanediamine was determined as the level of exposure at which no organ injury was observed (20) . These animal studies suggest that repeated exposures (3- days) to extremely high levels of polyamine vapor (concentrations well above the measured maximumair concentration (3.21 mg/m3) of the polyamine compound emitted

Lalita Bharadwaj, Ph.D. 20 November 10, 2009Health Human Risk Assessment from measured at 24 hours) may result in damage to the lung, kidney and liver. Occupational asthma has been reported in one industrial setting where shellac handlers were exposed to 1,2-ethanediamine vapor. However, the levels and duration of exposure to 1,2-ethanediamine vapor were not indicated in this report of occupational asthma (21) . Thus, it is difficult to assume a dose-response relationship for this health outcome. Both 1,2-ethanediamine and diethylenetriamine vapor have been reported to cause pulmonary edema after acute high level inhalational exposure (22) suggesting that short-term high levels of exposure may result in respiratory toxicity. Additionally, individuals who have been diagnosed with allergies or respiratory disease may be more susceptible to acute exposures to volatile polyamine compounds. Reproductive toxicity studies using pregnant mice indicate that high levels of oral exposure (400 mg/kg/day) during gestation days 6-13 will result in slight alterations in the birth weight . Maternal toxicity was not observed in this study suggesting that relatively high levels of oral exposure to 1,2-ethanediame are well tolerated by dams and only slight reproductive effects are induced. Although, inhalational reproductive studies were not performed, it is expected that reproductive effects would only be observed at extreme levels of exposure to 1,2-ethanediamine vapor and other related polyamine compounds (23) . Diethylenetriamine was evaluated by mutagenicity in the Salmonella/microsome preincubation assay using a standard protocol approved by the National Toxicology Program . Diethylenetriamine was negative in these tests suggesting that diethethylenetriamine is unlikely a mutagen (24) . Animal toxicity studies indicate that dietary exposures to diethylenetriamine are well tolerated due to the high NOEL determined through a subchronic toxicity study. The subchronic toxicity of diethylenetriamine was evaluated in a 90-day dietary study in the rats. Concentrations of 7,500 and 15,000 ppmdiethylenetriamine resulted in dose related pathologic effects in the liver and kidney. A no observable effect level was determined as 1,000 ppm(25) . Lalita Bharadwaj, Ph.D. 21 November 10, 2009Health Human Risk Assessment The dermal oncogenic activity of diethylenetriamuie was evaluated with both the high purity and commercial grade product. In a dermal toxicity study 25 ul aliquots of 5% aqueous solutions were applied to the backs of mice for three days each week for the lifetime of the animals. Approximate doses were 1 .25 milligrams for diethylenetriamine in high purity. No treatment-related skin tumors were observed, nor were there any evidence of increased incidence of internal tumors, suggesting that diethyelentriamine has lowoncogenic potential . Overall there was no evidence of an oncogenic effect for diethylentriamine under these conditions of study (26) . 1,2-Ethanediamine is not mutagenic. 1,2-Ethanediamine did not produce positive, doserelated, mutagenic effects in mutation assays or in the sister chromatid exchange tests of Chinese hamster ovary cells routinely used to asses mutagenicity of industrial chemicals (27) . In addition, no positive effects of unscheduled DNA synthesis were observed in primary rat hepatocytes, another test used to evaluate mutagenesis, suggesting that 1,2- ethanediamine does not alter the regular production of DNA . Taken together these data suggest that 1,2-ethandiamine or diethylenetriamine are not mutagenic chemicals and they are not likely to be carcinogenic (27) . Currently these compounds are not classified as human carcinogens (28) . The National Institute for Occupational Safety and Health and ACGIH has assigned an eight-hour time weighted average (TLV-TWA®) of 1 ppm (4.0 mg/m3) to diethylenetriamine (29) based on its potential to cause skin and respiratory sensitization. The TLV-TWA of 4.0 mg/m3 will be utilized in the process of this risk assessment to evaluate potential risk associated with exposure to the maximum emission levels of pentamethyldipropylenetriamine (3.21 mg/m3) in this case. It is apparent that the maximum

emission levels of pentamethyldipropylenetriamine measured in air samples at 24 hours exceed the TLV-TWA® divided by 100 . It is also important to note that individuals diagnosed with allergies and respiratory disease may be susceptible to acute exposures to polyamine compounds. However, in most cases, respiratory and skin sensitivities were reported in individuals repeatedly exposed to occupational levels. Thus, consideration of these susceptible individuals in the general population as well as the Lalita Bharadwaj, Ph.D. 22 November 10, 2009Health Human Risk Assessment residential exposure scenario must be considered when assessing risk to potential exposure to pentamethylpropylenetriamine in this case. 4.0 DOSE-RESPONSE ASSESSMENT The relationship between the potential received dose and the probability of adverse health effects is evaluated in the dose-response step of the risk assessment process. The intention of this risk assessment is to determine the relationship between exposure to maximumindoor air VOC concentrations and the potential for an adverse human health effect . Possible durations of exposure will be considered below . 4 .1 Threshold Limit Values and Dose Response Assessment In order to determine whether the maximumindoor air concentrations for VOC emission products pose a significant health risk to an individual residing in a home insulated with

t comparison of this value was made with an exposure level that is considered to be acceptable ("safe") for human chronic long-termexposure. This "safe" level could represent the ACGIH-Threshold Limit Value-Time Weighted Average® = 100 (TLV-TWA® = 100) a NOEL = 100 or an exposure limit derived fromanother regulatory body such as NIOSH, or OSHA and were determined in the hazard identification step of the risk assessment process. Asafety factor of 100, applied to the TLV-TWA®or other derived exposure limits provides an ample margin of safety in this case. Thus, it is assumed here that a chronic lifetime exposure to levels of TLV-TWA®, NOEL or other relevant and appropriate exposure limit = 100 would not pose a significant health risk to occupants of a home insulated with There are several factors supporting the use of a relevant exposure limit, such as the TLV-TWA® = 100, as a reasonable comparative value for the current assessment of

Through the hazard assessment step of the risk assessment it was determined that pentamethyldipropylenetriamine does not pose significant inhalational toxicity under conditions where individuals would be exposed to low airborne Lalita Bharadwaj, Ph.D. 23 November 10, 2009Health Human Risk Assessment concentrations (inhalation being considered the primary route of exposure since the emission products are expected to exist primarily in the vapor phase) . The emission concentration of pentamethyldipropylenetriamine is not likely to produce significant adverse systemic injury, and animal toxicity data indicate the risk of significant adverse effects following acute, subchronic or chronic exposure to low-levels of triamine compounds is minimal . Effects of mucous membrane irritation, respiratory and skin sensitization were only reported in individuals following repeated daily exposures to occupational levels (> 4,0 mg/m3) . Additionally reviewof toxicity information indicates that any acute, subchronic and/or chronic toxicity was associated with high levels and the oral route of exposure. Finally, the dynamic chamber analysis demonstrates emission levels for pentamethyldipropylenetriamine are transient and at lowlevels. Therefore, the potential for exposures to concentrations and for durations of exposure that are associated with adverse effects are unlikely in this case. In any scenario, potential exposure is likely to be of short termduration to lowlevels, rapid high levels of absorption into the human body is not likely, the accumulation to acute toxic concentrations in the ambient air, and/or in the body following absorption, is also very low, and exposure should not lead to a chronic or an acute adverse outcome. Triamines, like pentamethyldipropylenetriamine are classified as occupational skin and respiratory sensitizers, however human exposures in this case would not represent those of an occupational scenario (long-term, daily exposure, over work career of 30 to 35 years) and thus suggests that risk of sensitization is not likely. Overall, exposure to maximum measured concentrations of pentamethyldipropylenetriamine is not likely to result in a received human dose that would result in adverse human health effects.

Lalita Bharadwaj, Ph.D. 24 November 10, 2009Health Human Risk Assessment 5 .0 EXPOSURE ASSESSMENT A chemical agent will not produce adverse effects in biological systems unless the agent (or agents metabolite) reaches appropriate sites in the body at a concentration and for a length of time sufficient to produce the adverse effect . Thus, whether a toxic response occurs is not only dependent on dose, but is also dependent on the chemical and physical properties of the agent, the exposure situation and the susceptibility of the subject . Thus to characterize fully the potential hazard associated with exposure to the emission products from , information on the exposure situation is also required. In the following section of this risk assessment the exposure to VOC emission products in general, will be addressed. This step of the risk assessment process is designed to describe and characterize the likelihood, the extent, the magnitude, the duration and the route of exposure to the VOC emission products identified in Section 1 .0. The likelihood and the extent of human exposure to VOC emissions from or insulation material in general, depend on several factors that include: [1] the chemical nature of the VOCproducts, [2] the characteristics of the residential structure (size and air-tightness of the house) and [3] the activity patterns of the residents, or time spent indoors and [4] the susceptibility of the exposed individuals (5) . These factors will be considered here to assess the degree of exposure to VOC products emitted from Generally, VOCproducts when released into the indoor environment of a residence are expected to exist solely as vapours (2,5) . Thus, the respiratory system constitutes the primary route of exposure to each of the VOC emission products identified through emissions testing. VOCvapours within the ambient atmosphere are likely to be degraded quickly (5) . For example, many VOC are degraded in the atmosphere by reaction with photochemically produced hydroxyl radicals. Typically, the estimated half-life for VOC vapours range between a few minutes to several hours. Therefore it is expected that in a home, these VOC emissions will be degraded, their ambient levels will decrease over time and accumulation to a potentially toxic level in the ambient air of a residential Lalita Bharadwaj, Ph.D. 25 November 10, 2009Health Human Risk Assessment building is not likely . Therefore, in this case, the duration of exposure to low-level emission products is relatively short and repeated exposure to maximum emission levels is not maintained and extended for long periods of time. Additionally, acute exposures to low-levels are not associated with adverse health impacts. In the worst-case scenario, the maximumpotential level of human exposure to VOC emitted from insulation could be as high as the maximumindoor air concentrations determined by dynamic chamber analysis and outlined in Table 1 . The maximumindoor air concentrations of VOCproducts emitted from are predicted based on a 500 m3 house with a ventilation rate of 0 .3 air exchanges/ hour (3) . By applying this lowestimate for air exchange rate, the dynamic chamber analysis provides a very conservative estimate for maximumindoor air concentrations of the VOC products. Thus, even immediately after application of the insulation, the actual maximumindoor air concentrations in most structures would likely be lower than those predicted through DCA and outlined above in Table 1 . Individuals would likely be exposed intermittently, for a short period of time in the case of a residential environment . It can safely be assumed that the actual level of human exposure to ` derived VOC emission products would be considerably lower than the maximumindoor air concentrations applied in the process of this risk assessment . The combined factors of lowlevels of VOCemission relative to safe levels, short duration of VOCemissions and the lowpotential for repeated chronic exposure by occupants, to levels associated with toxicity, suggest a lowrisk for adverse health effects posed by exposure to airborne emission products of 6 .0 RISK CHARACTERIZATION Risk characterization is the final step in the risk assessment process. It involves integrating all information developed through hazard identification, dose response assessment and exposure assessment (toxicity, measured air concentrations, exposure pathway information, inhalation route), for the purpose of estimating risk to humans . Throughout this assessment, procedures have been used to err on the side of caution in Lalita Bharadwaj, Ph.D. 26 November 10, 2009Health Human Risk Assessment estimating the potential health risk associated with lerived VOC emission products. This analysis has revealed that VOCproducts emitted,from . ._ notpose a health risk to individuals residing in buildings insulatedwith this material . Anumber of factors support this conclusion: [1] With the exception of pentamethyldipropylenetriamine, maximum airborne concentrations of VOCemission products are well below the safety guidelines applied in the process of this risk assessment . Airborne emission levels fall to zero or to levels substantially lower than the maximummeasured emission concentrations over a 24-hour period of DCA testing. Concentrations below guidelines indicate that potential exposures are not likely to result in health risk in exposed individuals. Although, maximum emission concentrations of pentamethyldipropylenetriamine were above the safety guidelines applied in the risk assessment, through reviewof toxicity information, it was concluded the maximumemission levels are not associated with adverse health effects and are considered safe levels for human exposure. [2] All VOC emission products from t concentrations determined through DCA are of low order toxicity, posses a low inhalational toxicity and have not been demonstrated to pose a significant carcinogenic risk to the general population at intermittent low

levels of exposure. [3] The VOCcompounds are likely to have a short half-life in ambient air; therefore the level of human exposure is likely to be considerably lower than the maximumpredicted indoor air concentrations considered in the analysis above. [4] Based on the decay pattern of the VOCproducts (up to 30 days), the concentration of VOC in the indoor air decrease rapidly over time and should not accumulate to a toxic Lalita Bharadwaj, Ph.D. 27 November 10, 2009Health Human Risk Assessment concentration in the home or in any other residential building. Therefore, a repeated and prolonged exposure to maximumemission levels is unlikely to occur or be maintained over extended periods of time suggesting a low risk for adverse health effects. Additionally, acute exposures to low-levels are not associated with adverse impacts to human health. [5] Exposure to maximumpotential indoor air concentrations of VOCemission products was demonstrated through the risk assessment process to possess a lowpotential for human health risk under the conditions of exposure outlined in the Exposure Assessment Section of this risk assessment . [6] Short-termexposure to emission products at high ambient air concentrations is more likely to induce acute and/or systemic adverse effects. Symptoms of mucous membrane irritation and central nervous systemdepression could occur under acute conditions, but symptoms would reversible upon removal of exposure. In this case, very short-term, intermittent, low-level exposure is more likely to occur, indicating a lowrisk for acute adverse health effects following exposure. Maximumemission concentrations do not persist and in general emission levels drop to well belowmaximumor to zero within 12 hours of DCA

. [7] Low-level exposures to VOC products emitted from ire not associated with acute or chronic adverse health effects. Thirteen VOCwere identified as emission products of' Presently there are no Canadian or U

.S. human exposure standards for total volatile organic compounds (TVOC), however a target of I mg/m3 and 5 mg/m3 respectively, are being discussed for indoor office environments. The European Community has prepared a target guideline value for TVOCof 0

.3 mg/m3 for office environments. Review of the dynamic chamber analysis of ' indicate that TVOC concentration at the 1 hour retest was 0 .477 mg/m3

. This TVOC concentration falls Lalita Bharadwaj, Ph.D. 28 November 10, 2009Health Human Risk Assessment within the TVOC range of I mg/m' and 5 mg/m3 proposed by Canada and the US for office environments. The TVOC level falls below the European Community target guideline of 0.30 mg/m3 within 12 hours of DCA analysis (0.13 mg/m3) . Dynamic chamber analysis revealed that the nature, number and airborne concentration of VOC products emitted from lrop rapidly over time. Overall, the concentrations ofairborne VOCand TVOC decrease rapidly over time and do not accumulate in ambient air to a toxic concentration. Thus in this case, exposure to maximumairborne concentrations of VOCor TVOC, will not pose a significant human health risk. Based on the integration ofall information presented in the steps of the risk assessment process, a residential occupancy time of2 hours has been recommended for rhe residential occupancy of2 hours applies to residents ofstructures insulatedwith this material . 7 .0 RECOMMENDATIONS Indoor exposures to VOC from building materials are of obvious concern. Since there are numerous sources of VOCin building material and home furnishings, it is clear that regulatory improvements to indoor VOC standards in residential buildings will not be achieved by singling out individual products, but rather through an assessment of all potential components of such residences. Significant improvements in the indoor air of individual VOCcould be achieved by establishing an overall limit in the amount of total VOC contributed by all housing materials used in the construction of newbuildings. This limit could then be maintained through adequate ventilation. The current risk assessment indicates that there is a lowhuman health risk associated with exposure to VOC emission products from Since no significant threat to health can be associated with a short-term exposure to low-levels of these emission products, levels are transient and do not persist at levels exceeding safety limits over the 30-day period of dynamic chamber analysis, it is suggested that a residential occupancy time of 2 hours be considered for- Vith a planned Lalita Bharadwaj, Ph.D. 29 November 10, 2009Health Human Risk Assessment assessment of all building materials, the use of' insulation should not pose an additional health risk to occupants of residential or commercial buildings. 8 .0 CLOSURE A Human Health Risk Assessment (HHRA) has been completed as authorized . This report has been prepared for the exclusive use of Quebec and its agents for specific application to the polyurethane product it has been prepared in accordance with generally accepted toxicological practices and no other warranty, express or implied, is made. Any use which a Third Party makes of this report, or any reliance on decisions to be made based on it, are the responsibility of such Third Parties. Dr. L. Bharadwaj accepts no responsibility for damages, if any, suffered by any Third Party as a result of decisions made or actions based on this report . I trust that this report fulfils your requirements for this project. Should you require additional information, please contact Dr. Lalita Bharadwaj . Yours very truly, Lalita Bharadwaj, Ph.D. Toxicologist College ofNursing 107 Wiggins Road University of Saskatchewan Saskatoon, Saskatchewan S7N 5E5 Email : Ialita.bharadwaiCc)usask .ca I Phone: 966-1490 Date: November 10, 2009

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Lalita Bharadwaj, Ph.D. 33 November 10, 2009