350983 

O P PT-2011-0182 

63130000019 

p. 27 

HUMAN HEALTH RISK ASSESSMENT 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 

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Health 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 Limit Values 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 VOC Emissions and Time of Detection . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 

Table 2 : Maximum Measured Concentrations and Threshold Limit Values . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 

Lalita Bharadwaj, Ph.D . i 

November 10, 2009 
Health 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 VOC emissions 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 VOC products emitted. 

Lalita Bharadwaj, Ph .D . ii 

November 10, 2009 
Health 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 VOC emission products measured 

within 1 hour of dynamic chamber analysis were found to be well below the 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 

maximum emission concentrations were below the 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 low risk 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 of structures insulated with this material. 

Lalita Bharadwaj, Ph .D . 

November ]0, 2009 
Health 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 from a 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 low levels 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 maximum likely 

exposures to VOC emission 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, 2009 
Health 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, VOC emissions 

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 from a test specimen of a polyurethane product that has aged for approximately 

20 to 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 from commercial formulations of PU spray foam insulation. The results 

obtained by dynamic chamber analysis of PU foam products 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 VOC emission 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, 2009 
Health 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 CarbotrapTM 400 absorbent tubes, in conjunction with gas chromatography-mass 

selective detector analysis ; the number, chemical nature and the relative concentrations of 

VOC products emitted from the 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 from 0.019 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 

VOC emission 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 VOC detected. 

Lalita Bbaradwaj, MD. 3 

November 10, 2009 
Health Human Risk Assessment 

The results obtained by dynamic chamber analysis are summarized below and 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 DCA contained all 13 VOC emissions . 

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 VOC emissions profile identified at the 1-hour retest were 

similar in nature to the emissions profile identified in samples collected in the initial 42-

minutes of testing. 

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 of testing. 

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, 2009 
Health 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 low levels (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 

DCA testing 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 maximum airborne VOC concentrations emitted from 

were generally identified in air samples collected at the initial 42-minute period of DCA 

testing. Airborne VOC concentrations 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 

maximum measured airborne concentrations . 

A review of the DCA analyses indicate that erived VOC products 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, 2009 
Health 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 VOC products 

emissions drop to undetectable within 12-hours of DCA. 

In general, the magnitude of VOC emissions 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 of each VOC product decrease to zero 

within 12 hours and the emissions are transient and not maintained over the 30-day 

period ofDCA testing. 

The maximum indoor air concentrations of each VOC emission product and the time in 

which these levels were detected through DCA of ` 4) are summarized 

in Table 1 . The maximum measured 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, 2009 
Health Human Risk Assessment 

Table 1 : Maximum Indoor Air Concentrations of VOC Emission Products 

from id Time of Detection. 

VOC _Emission Product 

Identified 

Maximum Indoor 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 SRC report [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 VOC products from 

are initially emitted at low levels and would ultimately fall to undetectable levels within 

24 hours after its application. 

The maximum indoor 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, 2009 
Health Human Risk Assessment 

"Sealection 500" 

The time in which maximum VOC concentrations were detected specifies the 

point in time when maximum concentrations 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 VOC emissions derived from 

The toxicity of each VOC emission 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 of the 

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November 10, 2009 
Health 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-term exposure 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, VOC emission products 

were evaluated for their safety through review of 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. 

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November 10, 2009 
Health 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, 2009 
Health Human Risk Assessment 

3.0 HAZARD IDENTIFICATION 

This section summarizes the contaminants of potential concern that were selected for this 

assessment . A review of DCA of indicated that there were 13 VOC 

emitted from the polyurethane foam insulation product. The VOC emitted were primarily 

classified as aliphatic and aromatic hydrocarbons. The maximum measured 

concentrations of each VOC emitted 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) from the 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 VOC to 1 % of the 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 VOC emission products were considered to demonstrate a potential to 

cause adverse health outcomes under prolonged or repeated exposure. Table 2, 

summarizes the VOC emission products identified as COPC, their maximum measured 

concentrations and their respective ACGIH TLV-TWA values divided by 100. 

Lalita Bharadwaj, Ph.D. 11 

November 10, 2009 
Health Human Risk Assessment 

Table 2 : Maximum Indoor Air Concentrations of VOC Emission Products 

from and ACGIH TLV-TWA (regulatory limit) =100. 

VOC Emission Product 

Identified 

Maximum Indoor 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 

ACGIH TLV-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 ppm or 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-TWA for 1,4-Dioxane 

`ACGIH TLV-TWA for 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: Table Z-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 of February 10, 2004: 

http ://www.gpoaccess .gov/ecfr ] 

'ACGIH TLV-TWA for propylene glycol monomethyl ether 

'ACGIH TLV-TWA for Diethylenetriamine 

As summarized in Table 2, the 13 VOC emission products emitted from' 

have available ACGIH TLV-TWA for comparative purposes . The maximum measured 

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, 2009 
Health 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-term and/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 

COPC and were not considered further in the risk assessment process. 

As detailed in Table 2, the maximum emission 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, 2009 
Health 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 review of the chemical and animal/human toxicity data was outlined for the 

VOC emission 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 VOC emission 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 VOC emissions 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, 2009 
Health 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 VOC emission 

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 maximum airborne 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 below the 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 

below in Section 3 .2 under the heading 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 maximum measured 

airborne concentration of pentamethyldipropylenetriamine was 3 .21 mg/m3 respectively . 

The maximum airborne concentration of this VOC emission 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 maximum airborne 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, 2009 
Health 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. Maximum measured 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 

low levels . 

Amines are organic compounds that contain a basic nitrogen atom and 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, 2009 
Health 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 low to 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 from their 

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 of this 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 of diethylenetriamine in 

the environmental media of air, water and/or soil and therefore, the levels of exposure to 

Lalita Bharadwaj, Ph.D . 17 

November 10, 2009 
Health 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, metabolism and 

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, 2009 
Health 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-term repeated 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, 2009 
Health 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 below and 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 maximum air concentration (3.21 mg/m3) of the polyamine compound emitted 

Lalita Bharadwaj, Ph.D . 20 

November 10, 2009 
Health 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 ppm diethylenetriamine 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, 2009 
Health 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 low oncogenic 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, 2009 
Health 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 

maximum indoor 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 maximum indoor 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-term exposure. 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 from another 

regulatory body such as NIOSH, or OSHA and were determined in the hazard 

identification step of the risk assessment process. A safety 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, 2009 
Health 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 review of 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 low levels . 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 term duration to low levels, 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, 2009 
Health 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 VOC products, [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, VOC products 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. VOC vapours 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, 2009 
Health 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 maximum potential level of human exposure to VOC 

emitted from insulation could be as high as the maximum indoor air 

concentrations determined by dynamic chamber analysis and outlined in Table 1 . The 

maximum indoor air concentrations of VOC products emitted from are 

predicted based on a 500 m3 house with a ventilation rate of 0.3 air exchanges/ hour (3) . 

By applying this low estimate for air exchange rate, the dynamic chamber analysis 

provides a very conservative estimate for maximum indoor air concentrations of the VOC 

products . Thus, even immediately after application of the insulation, the actual 

maximum indoor 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 maximum indoor 

air concentrations applied in the process of this risk assessment . The combined factors of 

low levels of VOC emission relative to safe levels, short duration of VOC emissions and 

the low potential for repeated chronic exposure by occupants, to levels associated with 

toxicity, suggest a low risk 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, 2009 
Health Human Risk Assessment 

estimating the potential health risk associated with lerived VOC 

emission products . 

This analysis has revealed that VOC products emitted, from . ._ not pose 

a health risk to individuals residing in buildings insulated with this material. 

A number of factors support this conclusion : 

[1] With the exception of pentamethyldipropylenetriamine, maximum airborne 

concentrations of VOC emission 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 maximum measured 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 review of toxicity information, it was 

concluded the maximum emission 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 VOC compounds 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 maximum predicted 

indoor air concentrations considered in the analysis above. 

[4] Based on the decay pattern of the VOC products (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, 2009 
Health Human Risk Assessment 

concentration in the home or in any other residential building. Therefore, a repeated and 

prolonged exposure to maximum emission 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 maximum potential indoor air concentrations of VOC emission products 

was demonstrated through the risk assessment process to possess a low potential for 

human health risk under the conditions of exposure outlined in the Exposure Assessment 

Section of this risk assessment . 

[6] Short-term exposure 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 system depression 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 low risk for acute 

adverse health effects following exposure . Maximum emission concentrations do not 

persist and in general emission levels drop to well below maximum or 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 VOC were 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 TVOC of 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, 2009 
Health 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 of airborne VOC and TVOC decrease rapidly over time and 

do not accumulate in ambient air to a toxic concentration. Thus in this case, exposure to 

maximum airborne concentrations of VOC or TVOC, will not pose a significant human 

health risk. Based on the integration of all information presented in the steps of the risk 

assessment process, a residential occupancy time of 2 hours has been recommended for 

rhe residential occupancy of 2 hours applies to residents of structures 

insulated with this material. 

7.0 RECOMMENDATIONS 

Indoor exposures to VOC from building materials are of obvious concern. Since there 

are numerous sources of VOC in 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 VOC could be achieved by establishing an overall limit in the amount of total 

VOC contributed by all housing materials used in the construction of new buildings. 

This limit could then be maintained through adequate ventilation. 

The current risk assessment indicates that there is a low human 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, 2009 
Health 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 of Nursing 

107 Wiggins Road 

University of Saskatchewan 

Saskatoon, Saskatchewan 

S7N 5E5 

Email: Ialita .bharadwaiCc)usask .ca 

I Phone: 966-1490 

Date: November 10, 2009 

Lalita Bharadwaj, Ph.D . 30 

November 10, 2009 
Health Human Risk Assessment 

9.0 REFERENCES: 

l . Canadian Environmental Protection Act (1994) Human Health Risk Assessment for 

Priority Substances . ISBN 0-662-22126-5. Cat. No. En40-215/41 E. Health Canada On 

Line: http ://www.hc-se . c.g ca/eni7lish/index .html 

2. US EPA (1989) Risk Assessment Guidance for Superfund Volume 1 Human Health 

Evaluation Manual (Part A) . EPA/540/1-89/002 . 

3. National Research Council : Canadian Construction Materials Center (CCMC) 

National Standard of Canada. CAN/ULC-S705.1-01-Standard for Thermal Insulation 

Spray Applied Rigid Polyurethane Foam, Medium Density, Material-Specification . 

CAN/ULC-8774-09-Standard Laboratory Guide for the Determination of Volatile 

Organic Compound Emissions from Polyurethane Foam. 

4. Brad Boyle, Saskatchewan Research Council, Building Performance and Alternative 

Energy andManufacturing Division. (October 2009) Confidential Report : VOC 

Emissions Profiling of a Polyurethane Foam Sample for Demilec Incorporated . 

Prepared for : Mario Charlebois, Demilec Incorporated Boisbriand Quebec. SRC 

Publication No.12650-1C09, October, 2009. 

5 . Amdur, M.O., Doull, J., Klaassen, C.D., Casarett and Doull's Toxicology: The Basic 

Science of Poisons 4'h edition. Pergamon Press New York, New York 1991 . 

6. The American Conference of Governmental Industrial Hygienists. 2000 TLVs® and 

BEIs : Threshold Limit Values for Chemical Substances and Physical Agents and 

Biological Exposure Indicies . http ://www.ac ig h-org 

7. Institute for Occupational Safety and Health (NIOSH) Pocket Guide to 

Chemical Hazards website: h-ptt ://www.ede .gov/niosh/npg/np .g html. 

8. US Department of Labor Occupational Health and Safety Administration . 

httn ://www.osha.g_ov 

9. Snyder, R., Andrews, L. ., (1996) Toxic effects of solvents and vapors . In Cassarett 

and Doull's Toxicology : The Basic Science of Poisons (C .D. Klaassen, Ed.) . McGraw 

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10. Boublik T et al ; (1984) The Vapour Pressures of Pure Substances. Amsterdam, The 

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11 . NIOSH; National Occupational Exposure Survey (1985) . 

12. Sullivan, J.B. Jr., G.R. Krieger (eds .) . Hazardous Materials Toxicology-Clinical 

Principles of Environmental Health . Baltimore, MD: Williams and Wilkins, 1992., p. 

780. 

Lalita Bharadwaj, Ph.D . 31 

November 10, 2009 
Health Human Risk Assessment 

13 . Clayton. G.D., F.E. Clayton (eds .) Patty's Industrial Hygiene and Toxicology . 

Volumes 2A, 213, 2C, 2D, 2E, 2F: Toxicology. 4th ed . New York, NY : John Wiley & 

Sons Inc., 1993-1994., p. 1142. 

14. American Conference of Governmental Industrial Hygienists, Inc. Documentation of 

the Threshold Limit Values and Biological Exposure Indices. 6th ed. Volumes 1, 11, 

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15 . Grant, W.M. Toxicology of the Eye. 3rd ed. Springfield, IL : Charles C. Thomas 

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16 . Clayton, G. D. and F. E. Clayton (eds.) . Patty's Industrial Hygiene and Toxicology : 

Volume 2A, 2B, 2C: Toxicology . 3rd ed. New York: John Wiley Sons, 1981-1982., 

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17. Gosselin, RE., R.P. Smith, H.C. Hodge. Clinical Toxicology of Commercial 

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Hazardous Industrial Chemicals Safety Manual . Tokyo, Japan : The International 

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Hazardous Materials Toxicology-Clinical Principles of Environmental Health . 

Baltimore, MD: Williams and Wilkins, 1992., p. 779 

18. Grant, W.M. Toxicology of the Eye. 3rd ed. Springfield, IL: Charles C. Thomas 

Publisher, 1986., p. 336. 

19. Clayton, G. D. and F. E. Clayton (eds .) . Patty's Industrial Hygiene and Toxicology : 

Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982., 

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21 . Nakazawa T, Matsui S (1990) Ethylenediamine-induced late asthmatic responses. 

Journal of asthma, 27 :207-212 . 

22. Gelfand H (1963) Respiratory allergy due to chemical compounds encountered in the 

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381 . 

23 . Hardin B, Schuler R, Burg J, Booth G, Hazeldean K, MacKenzie K, Piccirrillo V, 

Smith K (1987) Evaluation of 60 chemicals in a preliminary developmental toxicity 

test . Teratogenesis, Carcinogenesis, Mutagenesis, 7:29-48 . 

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Lalita Bharadwaj, Ph.D. 32 

November 10, 2009 
Health Human Risk Assessment 

25 . Snyder, R. (ed.) . Ethyl Browning's Toxicity and Metabolism of Industrial Solvents. 

2nd ed. Volume I1 : Nitrogen and Phosphorus Solvents. Amsterdarn-New YorkOxford : Elsevier, 1990., p. 62 . 

26. Slesinski R, Guzzie P, Hengler W, Watanabe P, Woodside M, Yang R (1983) 

Assessment of genotoxic potential of ethylenediamine: in vitro and in vivo studies. 

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28 . IPCS (1993) International Chemical Safety Card -- Ethylenediamine. Geneva, World 

Health Organization, International Programme on Chemical Safety (ICSC 0269). 

29. American Conference of Governmental Industrial Hygienists TLVs and BEIs. 

Threshold Limit Values for Chemical Substances and Physical Agents and Biological 

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Lalita Bharadwaj, Ph.D . 33 

November 10, 2009