1 The views expressed in this paper are solely those of the author and do not represent the policies of the U.S. EPA. Mention o f trade names of commercial products should not be interp reted as an endorsement by the U.S. EPA
2 These comments are those of the CPSC staff and have not been reviewed or approved by, and may not necessarily reflect the views of, the Commission.



# Lessons Learned from the Federal Partners Workgroup on Spray Polyurethane Foam ( SPF )

KATHERINE SLEA SMAN 1
U.S. Environmental Protection Agency (EPA) 1 201 Constitution Ave., NW Washington, DC 2 0460 MELANIE BIGGS 2 Consumer Product Safety Co mmission ( CPSC ) 5 Research Place Rockville, MD 20850

ABSTRACT In 2009, the Environmental Protection Agency ( EPA ) convened a multiagency collaboration with the Occupational Safety and H ealth Administration (OSHA), the National Institute for Occupational Safety and Health (NIOSH), and the Consumer Product Safety Commission (CPSC) (collectively, “the Federal Partners”) to evaluate and address potential exposures to isocyanates and other chemicals during installation of spray polyurethane foam (SPF) insulatio n and air sealants in homes and schools. Commercial and Do

- It

- Yourself (DIY) applicators, as well as building occupants
, are often unaware of inhalation and dermal hazards. Applicators and others at the work site may not wear adequate personal protective e quipment (PPE). Building occupants, who remain on the premises during the operations or re

- enter ( re

- occup y ) the site before the product is fully cured
, may be at risk. For several years, t he federal agencies have been working with the polyurethanes industry to ensure accessible hazard communication, PPE, applicator , assistant, weatherization training, and best workplace practices to prevent exposure to isocyanates and other SPF chemicals. In addition, the F ederal Partners, in collaboration with othe r organizations, have identified critical information gaps and research needs to assess and measure exposures during use and curing of SPF products. This paper will discuss the progress of the S PF workgroup efforts to work with industry to establish best p ractices and encourage research on exposure to the chemicals emitted during and after the application of SPF.

INTRODUCTION/BACKGROUND

Spray polyurethane foam (SPF) insulation used in homes, schools, and other public buildings is a potential source of

ex posure to a complex and varied mixture of chemical substances. SPF is formed by a chemical reaction of two component parts, commonly referred to as Side A and Side B. Side A contains methylene diphenyl isocyanate (MDI), consisting of monomeric MDI, as well as higher molecular weight oligomers; and Side B contains polyols and a mixture of other chemicals, including catalysts, flame retardants, blowing agents, and surfactants. Polyurethane polymers are formed by reacting di

- or poly isocyanate s with polyol s. Depending on the polyurethane product being produced, the polyol side include s a complex proprietary formulation of polyo ls, flame retardants, surfactants, cross

- linking agents, chain extenders, catalysts, blowing agents, pigments, fillers, or other ingredients [1]. These chemicals may continue to emit at different rat es after application , depending on the extent of the rea ctions
, and may lead to adverse health effects if re

- occupancy occurs before the product is fully cured . SPF ingredients are recognized as presenting respiratory hazards in the workplace
, and when SPF insulation and sealants are applied on

- site in a home o r school, those same concerns could apply to other trade workers and consumers [2]. The magnitude and extent of exposures to SPF emissions is also highly variable and depends on many factors, such as formulation, environmental conditions, and method of appl ication. Thus, exposures to chemicals emitted from SPF through vapors, aerosols, particulates, and dust, during and after product application, are possible both short and long term. O ver the past several years
, to address potential exposure to workers and consumers , the F ederal P artnership and each of its member agencies, including EPA, CPSC, OSHA, and NIOSH have achieved many of the workgroup’s goals in supporting exposure reduction to various chemicals in SPF.E N VIR ONMENTAL PROTECTION AGENCY (EPA)

EPA’s mission is to protect workers and consumers from the risks associated with chemicals under the authority of the Toxic Substance Control Act (TSCA)

. The law ’ s goal is to ensure that chemicals sold and used in the United States do not pose an unreasonable r isk to huma n health and the environment. The law covers production and distribution of commer cial and industrial chemicals. TSCA allows EPA to establish reporting, record keeping, testing, and control

- related requirements for new and existing chemicals

. U n der this law’s authority
, EPA published an Action Plan on isocyanates in 2011, continues to review isocyanates through the New Chemicals’ program, and request ed information from the polyurethane industry on
t he “curin g” of poly urethane products. EPA also r elies o n the authority of the Pollution Prevention Act (PPA) to focus industry, government, and public attention on cost

- effective changes in production, operation, and raw materials use. Source reduction promotes practices that reduce the generation and u se of hazardous substances before recycling, treatment
, or disposal

. EPA and the F ederal P artners ha ve continued to work with industry to develop best practices for application of SPF
, and the Office of Research and Development (ORD) has been developing me thods to measure emissions of isocyanates and other chemicals from SPF as part of the ASTM Indoor Air Subcommittee D.22.05 on Spray Polyurethane Foam (SPF) Insulation

. Furthermore, under the authority of the Clean Air Act (CAA) and TSCA
, EPA reviews and ap proves the blowing agents used in SPF. EPA also initiated voluntary program s under the CAA for insulation materials.

EPA’s New and Existing Chemicals Program

Under EPA’s New Chemicals P rogram, EPA groups chemicals with shared chemical and toxicological properties into categories for premanufacture notice (PMN) reviews to facilitate the risk assessment decision process

. EPA categories include isocyanates, aldehydes, amines, and anionic surfactants. EPA considers all PMNs, including substances that f all wi thin such categories, on a case

- by

- case basis
, by examining structural and physical

- chemical properties and the Structure Activity Relationship (SAR) to support concerns for health or environmental effects [3]

. For any new chemical substance, if EPA determ ines, under TSCA section 5(e), that the substance “ may present an unreasonable risk of injury to health or the environment,” the PMN substance can be subjected to appropriate control actions and/or testing. This “may present” finding is developed through t he application of category

- based and/or case

- by

- case assessment of hazard endpoints and exposure
assessment s . For example
, under the New Chemicals P rogram , the isocyanate s ’ structure and health hazards are well

defined to use for assessment by the Agency. Isocyanates are defined as any molecular structure containing two or more isocyanate groups R

- (N=C=O). Members of the class include new isocyanate monomers
, as well as new oligomers, polymers, prepolymers, or reaction products of existing isocyanat e monome rs. Most new chemical isocyanates of concern are polymers or oligomers containing well

- known diisocyanate monomers
, such as toluene diisocyanate (TDI) or 4,4'

- MDI
, because they are potential dermal and res piratory sensitizers and can cause pulmonary toxici ty [ 4 ]

. As described under the category, an industrial hygiene (IH) and sa fety program should be followed to protect workers in workplaces where individuals handle isocyanates , c oatings
, or other formulations . Important components of this program should include: hazard communication and training on safe handling practices; use of efficient and well

- maintained application equipment, engineering controls and PPE ; and housekeeping procedures
, including spill

- prevention and cleanup practices . There should als o be means to measure airborne levels of polyisoc yanates and isocyanates. During spray applications, workers should take precautions to avoid breathing vapor s, mists
, or aerosols [ 4 ]

. For example, In 2015 , E PA issued a Significant New Use Rule (SNUR) un der the New Chemicals P rogram to mitigate worker and consumer exposure s to isocyanates. This rule outlines that any use of isocyanates in a consumer product must be reviewed by the New Chemicals P rogram, workers must have respiratory protection where they are “reasonably likely to be exposed” via inhalation routes, and any use involving an a pplication method that generates a va por, mist, or aerosol must be revi ewed through the New Chemicals P rogram [ 5 ].

Under EPA’s Existing Chemicals P rogram, EPA addres sed its concerns regarding these compounds in the Action Plans on MDI, TDI, and related compounds
, published in 2011. The Action Plans list a variety of regulatory and risk management actions the Agency could consider u nder TSCA sections 4, 5, and 6 to col lect information and m itigate risks associated with isocyanates. The Action Plans were based on EPA’s initial review of readily available use, exposure, and hazard information

on isocyanates . EPA considered which of the various authorities provided under T SCA and other statutes might be appropriate to address potential concerns with isocyanates. The Action Plan s described the courses of action the Agency planned to pursue in the near term to address its concerns. They did not constitute a final Agency deter mination or other final Agency action. Regulatory proceedings indicated by the Action Plan included appropriate opportunities for public and stakeholder i nput [2] . As a result of the Action Plans, EPA proposed a SNUR for TDI and related isocyanates in 2015
, designed to mitigate consumer exposures [ 6 ]

.A dditionally, under EPA’s Existing C hemicals program, in September 2012, EPA requested information
, from nine domestic manufacturers and processors of polyurethane chemicals
, relat ed to curing rates for poly urethane products intended to react further
, and thus
, undergo "curing" as part of their commercial use, such as use in adhesives, sealants, foams, coatings, and SPF. The curing rates for these types of products can affect the exposure potential for chemic als that may be formed as reaction products. Specifically, EPA requested information related to isocyanates. EPA wanted to know the curing time req uired to chemically react all isocyanate functional groups and the amount of time required, before and after a product has fully cured, to reoccupy a structure safely where these products have been used . This request in clud ed expected exposures to isocyanates, other formulation additives, and/or reaction products formed. In response to this request on curing, EPA received I H studies, proprietary information on formulations, and a risk assessment related to re

- occupancy. However, despite the information assembled
, uncertainty remains around curing time, the identification of other chemicals that may be emitted from SPF during and after curing, and the consumer re

- occupancy. For data received specific to SPF, chamber study results were submitted that tested for only a limited set of volatile organic compounds ( VOCs ) based on the California 01350 standard and ASTM Sta ndard Guide D 5116

- 06 [ 7 ]. Emission testing regarding when the consumer could
reoccup y the structure was rarely addressed in manufacturer’s responses . Additionally, t here was only one human health risk assessment specific to consumers regarding re

- occupanc y for consumers . This assessment based its conclusion on a limited set of VOCs and recommend ed a re

- occupancy time of 2 hour s for foam insulation [ 8 and 9 ].

EPA B est Practices

EPA maintains a robust website on SPF to help inform workers and consumers [1 ]

. EPA developed a best practices tool kit to educate professional SPF applicators on potential hazards and assist them in following workplace preca utions to prevent exposure to isocyanates and other potentially harmful chemicals. To accomplish this goal, EPA worked in partnership with the F ederal P artners, chemical and equipment suppliers, and other interested parties to identify cost

- effective practices and technologies. The development of technical facts sheets, case studies, and outreach materials to pr omote implementation of best health and safety practices was derived from the best practices work on automotive refinishing , which also involved exposure to isocyanates, as well as organic solvents, lead, and hexavalent chromium.

In 2011, EPA developed gu idance on ventilation principles and design considerations for SPF applications. As advised by EPA, w hen installing SPF, proper ventilation and controls must be implemented to protect the health of workers and occupants. Employing ventilation techniques du ring application, such as using local and general ventilation systems, can protect the applicant’s health. Additionally, p roper ventilation from efficiently supplied fresh air to the application area must be implemented after installation to protect the he alth of other trade workers and occupants from potentially harmful emissions of SPF chemicals (Fig ure 1). General exhaust ventilation systems typically consist of an exhaust fan, which pulls air out of the room and discharges it outdoors. General exhaust v entilation, also known as “dilution ventilation,” dilutes contaminated air by mixing it with cleaner room air. However, general exhaust systems are not recommended as the sole source of ventilation when hazardous vapors or mists are present because they do not immediately remove contaminants.

For an SPF installation, a local exhaust system would be appropriate during the application process to capture vapors, mists, dusts, and particulates at the source because they are emitted during the spraying and trim ming processes. When designing a ventilation system, it is important to consider these factors: ( 1) the work space , room, or enclosure to be exhausted ; ( 2) the exhaust system, including a hood or exhaust vent, ductwork, and fan that captures contaminants a t the source and transports them to a location outside the building away from HVAC air intakes and occupied areas ; and ( 3) getting fresh air to the room or work area that replaces the exhausted air. Ventilation combined with use of PPE will result in less worker exposure to the SPF chemical mixture. Following application, g eneral ventilation is appropriate to ventilate the entire work area and building before other workers or occupants enter the area; however, other workers entering the space may still need PPE to prevent exposure [ 10 , 1 1 , 1 2
, and 1 3 ]

.F igure 1

. Diagram of air flow [1].

Careful ly observ ing best practices and controls to prevent exposures during SPF installation in commercial or residential settings is paramount because applic ation and production is occurring on site. Use of proper PPE, containment, ventilation, and proper clean

- up practices are also important in these settings.

Recent IH studies have incorporated EPA’s ventilation guidance and PPE requirements to analyze the ir effectiveness using a generic SPF formulation and commonly used SPF formulations [13]

. Three generic formulation s of SPF were created by the
p olyurethanes industry for ventilation research and to evaluat e methods to support proposals and standards under consideration by the ASTM Indoor Air Subcommittee D.22.05

. T he generic formulations do not belong to any one manufacturer/formulator but have the performance characteristics of typical 0.5

- pound (open

- cell foam) , 2

- pound (closed

cell foam) , and two compon ent kit SPF formulations [1 4 ]. In 2010, the ASTM D22 .05 subcommittee initiated work on SPF i nsulation emissions t o standardize spraying and sample preparation for SPF titled
, “ Standard Practice for Spraying, Sampling, Packaging, and Test Specimen Preparati on of Spray Polyurethane Foam (SPF) Insulation for Testing of Emissions Using Environmental Chambers (D7859)

. ” T o evaluate the impact of changes in ventilation rates on the concentration of SPF chemical vapor and particulates emitted during SPF application
, various industry studies have been conducted

. The studies have analyzed emissions from the chemicals in the generic formulation and commonly used formulation [13]
, including MDI ; catalysts
, such as d imethylethanolamine (DMEA) and N,N,N’ ;

- t rimethylaminoe thylethanola mine (TMAEEA) ; flame retardants
, such as tris

- (chloro

- 2

- propyl) phosphate (TCPP) ; blowing agents , including 1,1,1,3,3

- Pentafluoropropane ( HFC

- 245fa ) ; and VOCs through field sampling, spray booths, and small environmental chambers. Samples were taken during and after application for 4, 12, and 24 hours
, to determine possible exposures to workers and other trades. The s tudies concluded that ventilation and proper PPE for the applicator
, and possibly other trades
, is vital for protection during and after application [ 1 1 , 1 2
, and 1 3 ].

EPA developed checklists to describe safer work practices and strategies for helping to protect workers and building occupants and to promote the safe use of SPF insulation. To develop the checklist, EPA conducted a comprehensive literature review and had a series of targeted interviews with SPF applicators, trade associations, and industry representatives. The self

- evaluation checklist is a tool to help evaluate current practices and technologies used by manufacturer s and processors to identify areas where they should ma ke improvements to protect workers and residents/building occupants from potential exposures to isocyanates, amines, flame retardants, blowing agents, aldehydes, and other substances generated during S PF application. The checklist is designed to serve as a resource for manufacturers and processors to review, evaluate, and improve their work practices on a regular basis . Continuous improvement and adoption of the safer work practices identified by use of this t ool will help reduce worker exposures over time [1]

.Significant New Alternatives Policy (SNAP) Program

Blowing agents used in SPF and other polyurethane products previously consisted of chlorinated volatiles, such as trichlorofluoromethane (CFC

- 11) and other CFCs (chlorinated fluorocarbons). These were commonly used until the late 1990s when CFCs were phased out due to concerns about protecting the ozone layer and ozone depletion potential. Following the phase

- out, EPA created the Significant New Alternatives Policy (SNAP) Program under section 612 of the CAA amendments. SNAP evaluates alternatives to ozone

- depleting substances. Substitutes are reviewed on the basis of ozone depletion potential , global warming potential (GWP), toxicity, flamma bi li ty, and exposure potential [1 5 ]

. EPA also conduct s a P MN review, evaluating health and environmental hazards, under S ection 5 of TSCA for any substance that is considered a new chemical , including blowing agents [3]

. As of October 2014, EPA has approved bl owing agents for use in rigid polyurethane foam . S ome of the same blowing agents are also commonly used in SPF [ 1 6 ], such as HFC

- 245fa, which has a GWP of 950

− 1020 ( 100

- year time horizon ) [ 1 7 ]. However, the next generation of SPF blowing agents have recently been approved under the SNAP program [17 and 18].

Energy Star Residential

ENERGY STAR is a voluntary program established by EPA in 1992, under the authority of the CAA. Under Section103(g) of the Clean Air Act
, EPA is authorized to “ conduct a basic engineering research and technology program to develop, evaluate, and demonstrate non

– regulatory strategies and technologies for reducing air pollution. ” In 2005, Congress enacted the Energy Policy Act. Section 131 of the Act amends Section 324 of the Energy Policy and Conservation Act, and

“ established at the Department of Energy and EPA a voluntary program to identify and promote energy

- efficient products and buildings to reduce energy consumption, improve energy security, and reduce pollution through voluntary labeling or other forms of communication about products and buildings that meet the highe st energy efficiency standards. ” The ENERGY STAR program has encouraged the adoption of energy

- efficient products, practices, and services through partnerships, objective measurement tools, and consumer education. Through Energy Star’s R esidential P rogra m, insulation materials are evaluated

. EPA recently revised requirements for residential insulation manufacturers to participate in ENERGY STAR. As noted in the requirements, insulation manufacturers need to provide clear and specific safe installation
pra ctices and PPE, s afe reentry (re

- occupancy) times for home occupants after installation, and SDS s for chemical reactants with complete hazard information listed. In addition, all products must be third party certified for R

- values and fire resistance [1 9 ].

Indoor air P LUS

EPA also created Indoor airPLUS to help builders meet the growing consumer preference for homes with improved indoor air quality. Indoor airPLUS builds on the foundation of EPA's ENERGY STAR requirements for new homes and provides additio nal construction specifications to provide comprehensive indoor air quality. Construction specifications include installation of moisture control systems, conditioning systems, combustion

- venting systems, radon

- resistant construction, and low

- emitting buil ding materials [ 20 ]. The program released its guidance document titled, “ Healthy Indoor Environment Protocols for Home Energy Upgrades
, ” in 2011
, to provide guidance on improving and maintaining good air quality in the home. The document specifically a ddre sses best practices for worker installation of SPF to ensure good air quality in homes [2 1 ].

C ONSUMER PRODUCT SAFETY COMMISSION (C PSC )

CPSC’s mission is to protect the public from unreasonable risk s of injury and death associated with the use of consumer products. Among others, i ts authorities include the Consumer Product Safety Act (CPSA), Federal Hazardous Substances Act (FHSA), and t he Consumer Product Safety Improvement Act of 2008 (CPSIA), which amended the CPSA

.
Federal Hazardous Substances Act (F HS A )

Under the FHSA ( 15 U.S.C. 1261 )
, product manufacturers must determine whether their products are hazardous substances and if so, their products must be properly labeled. The FHSA defines a hazardous substance as a substance that is , among other char acteristics, toxic, corrosive, or an irritant and may cause substantial illness during any reasonably foreseeable storage, handling, or use

. Household p roducts , including those used or stored in a garage, shed, carport, or other building that is part of th e household
, are covered. The FH SA requires hazardous substances to bear labeling that alerts consumers to the potential hazards that those products present and tells them what they need to do to protect themselves and their childre n from those hazards.A mines Study

CPSC’s interest concerning SPF focuses on the health hazards and the synergistic and/or cumulative exposures from the various chemical ingredients used in SPF products. CPSC
, has received 40 incident reports from homeowners from 2005 to the present , after SPF was i ns t alled in their home by a contractor or by t hemselves

. These incidents include lingering odors in the house ; respiratory

- related problems ( i.e ., asthma, coughing) ; irritation ( e. g

. , eyes, throat) ; and headaches. In some instances
, residents moved out of their homes due to the severity of health effects they

r eportedly experienced. Homeowners are urged to file an online Consumer Product Incident Report with CPSC on the Saferproducts.gov websit e if they are experiencing adverse heal th effects believed to be due to SPF insulation

. Initially, CPSC staff focused attention on the isocyanates in SPF as the chemicals potentially causing these reported health effects. T he constituents that make up S ide A have generally been considered to p resent the greatest possible health hazard due to the well

- known potential of isocyanates to produce respiratory and dermal sensitization ( i socyanates are believed to be a leadi ng cause of work

- related asthma ) [2 2 ] . However, isocyanates are very reactive and may not be available for exposure . Therefore, the odors and adverse health effects identified after SPF installation may not be due to the isocyanates but to the chemicals making up the Side B, such as amine catalysts. Documented worker exposure s to ai rborne concentrations of amine catalysts may result in irritation of the respiratory system, skin, and eyes. Inhalation exposure may also cause a re versible effect known as glaucopsia, “bluehaze,” or “halovision” in the eyes. The health effects described i n owner complaints were similar to those associated with amine exposure; therefore, CPSC staff believed the odors identified after SPF was installed may be due to the amine catalysts in Side B

. However, exposure limits are not yet established for the major ity of the amine catalysts used in SPF systems [14]

. When SPF is applied according to the manufacturer’s instructions, the foam achieves a tack

- free state within a few minutes of application. Depending on the characteristics of the foam, such as the comp osition of the Side B chemicals, the heat dissipated during the exothermic reaction, and ambient conditions (temperature and humidity), it can take additional hours or days before the foam is fully cured and the optimum physical properties of the foam are achieved [ 23 ]

. Because s ome of the compounds and reaction by

- products ( i.e ., aldehydes) in SPF are expected to exist unreacted in the foam during this curing time ( e.g ., certain catalysts and blo wing agents), they may potentially be emitted from the installed foam and cause the noted health effects.

Therefore
, CPSC staff cho se five amine catalyst s representative of those used in SPF in the United States and assessed their available toxicological and exposure data . This assessment was complet ed to de termine what health effects could

occur from exposure to th e amine catalysts present in the three generic SPF formulation s developed by the ASTM Indoor Air Subcommittee D.22.05 mentioned above . The assessment concluded that observed consumer effect s are similar to those discussed for amine exposure in both laboratory animals and workers; and therefore, some of the described health effects may be due to exposure to amines from SPF

. However, SPF i s a complex mixture of MDI or MDI

- b ase d isocyanates, polyols, catalysts, blowing agents, fire retardants, and/or surfactants; therefore
, amines may not be the only chemical class producing the reported adverse health effects

. To determine exposure limits f or consumers, CPSC staff suggest ed that industry and the F ederal P artners perform exposure studies by varying exposure times and distances from spray sources. These results would provide additional exposure data to make determinations of potential health e ffects for consumers from SPF [1 4 ]

. Exposure Assessment Study

CPSC initiated an Interagency Agreement (IAG) with the National Institute of Standards and Testing (NIST) in 2013 to understand what compounds in SPF may be causing adverse health effects in consumers. The primary objective s of this study are to develop robust methods for testing SPF emissions and to identify and quanti fy the compounds released from SPF applied in residential settings. This IAG contribute s to the development of voluntary stand ards in t he ASTM Indoor Air Subcommittee D.22.05 on SPF Insulation , especially WK4029, a New Test Method for Estimating Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation Using Micro

- Scale Environmental Test Chambers [ 24 ]

. Th is research fou nd the release of a flame retardant ( TCPP) from SPF that was s prayed 1.5 years ago in the NIST Net Zero Energy Residential Test Facility (NZERTF) [ 25 ]

. Th ese data are the first to examine emissions from SPF after prolonged curing

. Eventually, t hese data and methods will aid in determining the compounds that may cause adverse health effects in consumers and the factors that may cause elevated releases of these compounds.N ATIONAL INSTITUTE FOR OCCUPATIONAL SAFETY AND HEALTH (N IOSH )

NIOSH ’s mission is to provide leadership in conducting occupational safety and health research to prevent work

- related illness, injury, disability, and death and developing and providing worker education and training. NIOSH led the development of methods for determining airb orne isocyanate exposures for the total reactive isocyanate group (TRIG)
, the issuance of several Alerts on the prevention of asthma and death from diisocyanate exposure
, health hazard evaluations on isocyanates

. In addition, NIOSH collaborated with the Ag ency of Toxic Substances Disease Registry (ATSDR) to investigate community exposure to isocyanates

.

DAN Method

NIOSH and the University of Massachusetts

- Lowell have developed a unique analytical metho d that c an be used to adequately assess the reactivity of the TRIG. Some methods measure oligomeric isocyanates in addition to diisocyanate monomers, even though analytical standards are not generally available for oligomeric species (NIOSH Method 5525, HSE Method MDHS 25/4). Individual isocyanate species in the sample produce peaks in the chromatogram, and these peaks can be summed to give a measure of Total Reactive Isocyanate Group (TRIG), which is the basis of the isocyanate Occupational Exposure Limits (OEL) in some countries [ 2 6 ]. In SPF products, MDI m onomer is the major isocyanate species in the formulation. However, the fast

- curing nature of the SPF means that MDI monomer and other oligomers present in the original isocyanate formulation are rapidly converting to intermediate isocyanate species. Estab lished chromatographic methods are not suited for measurement of these intermediate species. Summation of many peaks in a chromatogram is labor intensive for samples containing complex isocyanate mixtures. Moreover, not all isocyanate species in a sample e lute from the column or produce a measurable peak in the chromatogram. A sampling and analytical method based on derivatization with the reagent 1,8

- diaminonaphthalene (DAN) is fundamentally different than conventional chromatographic isocyanate analysis m ethods [ 2 2 ]. Like conventional methods, isocyanate species react with DAN upon sampling. However, rather than analyzing this derivatized isocyanate mixture, the mixture is treated with acid to catalyze an intramolecular cyclization that converts all DAN

- d erivatized isocyanate groups to a single molecule of 1H

- perimidin

- 2(3H)

- one (perimidone). This reaction is shown in Figure 2.

N H 2

N H 2 N

N H 2 H

N H H N 

## +

+ R N H 2 

## a c i d D A N

p e r i m i d o n e R
N

C
O

C O C O
N H
R 

## S t e p 1

S t e p 2

Figure 2 Reaction of DAN with isocyanates to yield the analyte perimidone

The DAN method has been shown to measure isocyana te groups accurately in aromatic isocyanate products ( MDI

- and TDI

based products ) [ 2 7 ]. The method is particularly suitable for measuring isocyanates in SPF because of the rapid curing of this material and the generation of intermediate isocyanate specie s. In a simulated spray of SPF insulation, side

- by

- side air sampling using NIOSH Method 5525 impingers and DAN impingers found approximately ten fold higher TRIG levels with the DAN impinger [ 2 8 ]. Future investigation with the DAN method will include measu rement of residual isocyanates on surfaces and in dust, the distinction between extractable isocyanate and chemically bound isocyanate, and the extent/rate of curing of SPF.NIOSH Alerts on Isocyanates

A NIOSH Alert in 1996, described seven cases of iso cyanate exposure , which revealed potentially serious respiratory disease s after exposures to isocyanates involving spray painting, spills, foam operation, application of roofing foam, wood product manufacturing, and coal mining

. The Alert is intended to re duce the potential for exposed workers due to the adverse health effects. The se case studies show the examples of isocyanate

- induced asthma, respiratory disease, and death.

The incidents resulting in death were attributed to worker exposure s. One death wa s attributed to exposure to two component polyurethane paint with TDI

. T he other death was a result of prolonged and chronic exposure to MDI while working in a foam operation facility that manufactured artificial plants , with poor ventilation. In another i ncident, two police officers developed asthma

- like symptoms after a truck carrying TDI spilled on a highway. Evidence of occupational asthma was also reported in spray painting operations and in wood products manufacturing. Furthermore, c oal miners were ex posed to MDI in rock glues resulting from improper application and were using air

- purifying respirators as opposed to supplied

- air respirators , which resulted in respiratory disease . In a n incident involving SPF application to a school roof, school staff w as exposed to isocyanates resulting in asthmatic reactions.

As a result of the reported incidents, NIOSH recommends product substitution to less hazardous material s , closed systems and ventilation to minimize exposure ; worker isolation to inhibit other tr ades from entering the work area ; and wearing PPE. However, as recommended by NIO SH
, respiratory protection should not be used as the primary source of exposure reduction to isocyanates
, and only the most protective respirators should be worn for potent se nsitizers and carcinogens
, such as a self

- contained breathing apparatus. Any respiratory program should also adhere to NIOSH and OSHA requirements
, which include training and medical surveillance ; fit testing ; environmental monitoring ; maintenance and insp ection ; proper storage ; and written operating procedures. Any potential worker exposure to isocyanates must be communicated to the worker through labeling and training on the SDS. In addition, m edical monitoring and incident reporting of isocyanate worker exposure should also be established [2 9 ]

. NIOSH also published an Alert in 2006 on the use of spray application of isocyanates for truck

- bed liners. The Alert concluded that isocyanates can cause contact dermatitis, skin and re s piratory tract irritation, immun e sensitization, and asthma [ 30 ]

.

Health Hazard Evaluations (HHE)

NIOSH’s H ealth Hazard Evaluations (H HE ) are conducted to learn whether workers are exposed to hazardous substance s based on requests from workers. For an HHE, NIOSH conducts an inv estigation or refers the incident to a more appropriate
agency. During the investigation, NIOSH will first discuss the worker ex posure situation with the employee or employer and
, if necessary
, perform a site visit . The site may include a tour of the workp lace, interviews, medical testing, or record review of exposure and health of the workers. Then, NIOSH will draft a written report of its finding s and recommendations that the employer is required to distribute to its employees [ 31 ]

. I n 2003, a HHE spray foam application for isocyanates was published from a request by the United Union of Roofers, Waterproofers and Allied Workers in Philadelphia, P A . The request involved employee exposures to MDI during the spray application of p olyurethane foam, and exposures to VOCs during a rubber roofing membrane installation and spray gun cleaning. Employees had reported respiratory symptoms
, such as difficulty breathing, coughing, chest tightness, and skin irritation. NIOSH investigators conclude d that a health hazard existed from exposure to MDI during the polyurethane foam application, and recommendations we re provided to reduce exposures to roofers during the spraying of MDI

- containing foam, including use of PPE [ 32 ]

. Biomonitoring and Fence line Exposure to Isocyanates

In the mid

- 1990s, ATSDR, NIOSH, and the North Carolina Department of Health and Human Services conducted an investigation into community exposure to TDI near a manufacturing facility using polyurethanes. The study evaluated whet her residents near the facility had increased asthma, antibodies specific to TDI, and whether there were detectable TDI levels in the air. However, even though the residents living near the facility had higher rates for asthma than the residents living far ther away from the facility it was not statistically significant, and symptom prevalence varied between the two communities. This may warrant further investigation into nonoccupational exposure to understand why community exposures were not notably differe nt. The study also revealed the lack of biomarkers for isocyanates. Of the more than 300 participants that provided blood samples, only one had a specific antibody for TDI. For other isocyanates, MDI and HDI were prevalent in both communities . This sugges t s isocyanate exposure from other sources, such as SPF or other polyurethane products [ 3 3 ]

.O CCUPATIONAL SAFETY AND HEALTH ADMINISTRATION (O SHA )

OSHA’s mission is in the development of safety and health standards, the enforcement of s tandards, assistance to States, and providing research, training, education, and information. OSHA oversees that employers meet their responsibilities for hazard communications, worker training, and the use of appropriate engineering and/or administrative control s, and PPE
, when necessary. SDSs are a critical aspect of hazard communication. OSHA recognizes that there may be current deficiencies and inconsistencies in SDS preparation and use. OSHA published the Hazard Communication Standard (HCS 2012) on Mar ch 26, 2012. The HCS 2012 aligned with the provisions of the United Nations’ Globally Harmonized System of Classification and Labeling of Chemicals (GHS). OSHA also initiated a National Emphasis Program (NEP) in 2013
, to identify and reduce or eliminate th e incidence of adverse health effects associated with occupational exposure to isocyanates , and developed a website on green jobs

.

Green Jobs

OSHA launched a n interactive website on Green Jobs ; “green jobs” are broadly defined by OSHA as jobs that help t he environment. One of the key green job workforce areas is weatherizing, insulating, and sealing , which are an important part of energy effic iency and conservation programs. There are v arious types of weatherizing, insulating
, and sealing products that in clude blow

- in a nd spray

- on applications. However, t he application or installation of these products may require a certain amount of training to apply these materials to product specifications and to achieve proper weatherization. The materials used in the se types of applications can include, but are not limited to: blow

- in, fiberglass and cellulose; spray

- on, SPF, spray polystyrene, and spray latex sealant. The OSHA site guides users through an understanding that although weatherization applications and ma terials have some benefits , a ll weatherization applications and materials have some hazards

. The hazard information and solutions common to all these applications and materials include: confined spaces, falls, electrical, medical and first aid, ventilatio n , proper PPE and respiratory protection [ 3 4 ]

. OSHA National Emphasis Program (NEP) and Hazard Communication

The Isocyanates NEP was developed in 2013 to focus OSHA resources on the workplace health issue of occupational exposure to isocyanates. The N EP combines enforcement and outreach efforts to raise awareness of employers, workers, and safety and health professionals of the serious health effects associated with occupational exposure to isocyanates. Workers in a wide range of industries are exposed to isocyanates known to be associated with work

- related asthma. Isocyanate exposure could result from activities involving painting, blowing foam insulation, and the manufacture and thermal degradation of many polyurethane products
, such as polyurethane f oam, insulation materials, surface coatings, car seats, furniture, foam mattresses, under

- carpet padding, packaging materials, shoes, laminated fabrics, polyurethane rubber, and adhesives. The NEP began in June 2013
, and will expire in June 2016 ; and durin g the course of the program, OSHA will randomly choose sites for inspections that target multiple polyurethane industries with a focus on general industry, maritime, and construction based on informati on from NIO S H ’s H HEs
, sampling data, known overexposure s, and worker compensation data. Sites may also be selected based on a complaint
, referral, or where potential worker exposure to isocyanates is suspected. OSHA will evaluate inhalation, dermal
, and other routes of occupational exposure to isocyanates
, usi ng the established permissible exposure limits ( PEL s ) , recommended exposure limits (RELs) by NIOSH, or OEL s by the American Conference of Industrial Hygienists (ACGIH) . During the inspection
, OSHA will collect air and wipe samples, request the site’s hazar d communication program, and assess PPE. This instruction supersedes all Regional and Local Emphasis Programs specifically addressing occupatio nal exposure to isocyanates [ 3 5 ]

.
In 2012, OSHA revised their HCS to align with the GHS . The revision to HCS pr ovides a coherent approach to classifying chemicals and communicating hazard information on labels and SDS [ 3 6 ]

. The standard classifies the potential hazard s of chemicals and requires that employers communicate information concerning hazards and appropri ate protective measures to employees, including developing and maintaining a written hazard communication prog ram for the workplace, which includes lists of hazardous chemicals present; labeling of containers of chemicals in the workplace ; labeling contain ers of chemicals being shipped to other workplaces; preparation and distribution of SDS to employees and downstream employers; and development and implementation of employee training programs regarding hazards of chemicals and protective

measures. As a res ult of the new GHS requirements
, the Center for Polyurethane Industry ( CPI ) and the Spray Polyurethane Foam Alliance (SPFA) developed a guidance document titled
, “General Hazard Communication Guidance for Spray Polyurethane Foam (SPF) Insulation Applicatio n.” The guide serves as an outline for manufacturers and processors to consider to develop a hazard communication program to comply with 29 CFR 1910.1200 [ 3 7

.COLLABORATION BETWEEN THE FEDERAL PARTNERS AND INDUSTRY

Since the creation of the F ede ral P artnership, the workgroup has identified the critical research needs to assess and measure exposure. These needs have been explored through the International Isocyanates & Health Conference and in the ASTM D22.05 Committee’s Symposium on SPF insulatio n

.

I nternational Isocyanates & Health Conference

An international conference on isocyanates and health was held in April 2013, where academics, industry, federal agencies, worker representatives, clinicians, and others convened to answer questions abou t whether there are health effects related to isocyanate exposure? How can isocyanate occupational exposures be measured and reduced, especially among workers in less

- regulated, often small

- scale enterprises in the United St ates and around the world? Can consumers also experience health effects from exposures to various household and do

- it

- yourself products?

The conference included plenary overviews and discussions, along with oral and poster presentations. The specific res earch findings covered six thematic areas:

• Worker and consumer exposure issues ;

• Toxicity testing, animal models, and biomarkers ;

• Human cancer risk ;

• Environmental exposure and monitoring ;

• Respiratory epidemiology and disease ; and

• Occupational health surveil lance and manageme nt

.

The identification of these themes and research priorities was derived from discussions with all stakeholders from meetings, targeted surveys, feedback from the conference’s abstr act presenters and invited spea kers, and peer

- reviewed input. During each of the presentations
, the current state of the science was discussed
, along with knowledge gaps and research priorities
to help understand worker and consumer exposures. For instance, under the area of worker and consumer exposures
, the major areas of research needs and priority areas were product testin g and exposure characterization, hazard/risk communication, and prevention of exposure and disease. For toxicity, biomarkers, and cancer risks
, it was demonstrated that there should be mo re research into modeling to investigate dose and routes of exposure for both animal and non

- animal modeling, validation of biomarkers, and identification of populations at risk and mechanistic data to understand causes of

cancer.

Improvements in environm ental exposure and monitoring were also presented . A variety of research needs were discussed to understand worker exposure
, including : air and dermal sampling; analytical methods; direct reading monitors; co

- exposures for both respiratory and dermal conta ct ; and measurements of degradation and emissions.

Finally, knowledge of respiratory epidemiology, disease, and occupational health surveillance were discussed
, including the need for additional epidemiology studies on workers to understand risk, biomarke rs, and health eff ects, improved diagnostic tests, and better surveillance procedures to institute workplace controls and management. As a result of the conference, it was recommended that a working group composed of all stakeholder groups continue to coll aborate to address gaps and facilitate funding needs , along with the suggestion that all stakeholders continue to promote best practices [ 3 8 ]

.
EPA, CPSC, the National Institute for Standards Technology (NIST), and Industry

– ASTM Indoor Air Subcommittee D.22.05 on SPF Insulation

Since 20 1 0
, t he ASTM Subc ommittee D.22.05 on indoor air has been working collaboratively to create standardized meth od s for measuring chemical emissions from SPF insulation

. D22.05 is focused primarily on developing methods to measure SPF emissions using micro

- and small

- scale chamber s

. These methods could be used for screening for emissions from SPF in residential or commercial buildings and for identifying the production of off

- spec ification foam.

The f inal and proposed stand ards considered by the D22.05 subcommittee include:

• Standard Practice for Spraying, Sampling, Packaging, and Test Specimen Preparation of Spray Polyurethane Foam

(SPF) Insulation for Testing of Emissions Using Environmental Chambers ( D7859);

• Test Method f o r Estimating Emissions of MDI from Spray Polyurethane Foam (SPF ) Insulation using Emission Cells or Micro

- Scale Environmental Test Chambers (WK43872);• Test Method for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF ) Insulation Samples in a Large

- Scale Spray Booth (WK 46527);

• Test Method for Determination of Vapor

- Phase Organic Compounds Emitted from Spray Polyurethane Foam

(SPF) Using Sorbent Tubes Analyzed by Thermal Desorption Gas Chromatography and Mass Spectrometry (WK40292) , and

• New Test Method for Estimating Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation Using

Micro

- Scale Environmental Test Chambers (WK40293)

The list of proposed and final standards represents the issues raised by the committee and the range of co mpounds of interest th at include isocyanates, blowing agents, amine catalysts, flame retardants, and aldehydes. The ongoing work of ASTM D22.05 aims to d evelop consensus method s to answer fundamental questions , such as : W hat is emitted ? W hat is the time

co urse of emissions ? W hat factors impact emissions and potential exposures ? H ow useful are emission factors developed in micro chambers for predicting concentrat ions i n full

- scale environments ? T o answer some of these questions
, the subcommittee held a sympo sium in April 2015. The Symposium on Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) will result in publication of Selected Technical Papers (STP) in 2016.

The objective of the s ymposium wa s to provide a forum for the exchange of ideas fro m SPF manufacturers, federal agencies, indoor air quality professionals, testing labs, air quality consultants, instrument v endors, and other stakeholders. The following mutual areas of interest to the Federal Partners, the SPF in dustry, and other stakeholders we re the focus of this symposium
, representing a continued dialog between f ederal agencies and t he SPF industry :

• r esearch and method development for measuring potential SPF emissions of semi

- volatile organic compou nds ( SVOCs ) and VOCs from SPF raw materials including isocyanates, blowing agents, amine catalysts
, and flame retardants, and from potential reaction or byproducts that may o r are anticipated to be formed ;

• f ederal and other governmental agencies’ regulato ry approaches and supporting investigation, assessment, and research needs ;

• m odeling, scaling up from lab to large

- scale chambers or buildings ;

• i nternational perspective on regulation and testing of SPF insulation emissions ;

• i ndustry perspective/needs an d product stewardship activities ;

• f ield investigations or large

- scale chamber/spray booth studies to evaluate emissions or ventilation rates, and

• a ppl ication of the knowledge from product emissions data/research to practice ( e.g. , stewardship commitment, green building practices, codes for residential ventilation and global leadership).

EPA is investigating research needs and approaches for the ASTM Committee to measure MDI . EPA and CPSC
, through NIST
, are investigating chamber methods used to measure c hemicals in SPF, including amine catalysts and flame retardants

. CPSC, through NIST
, is evaluating emission s of the flame retardant TCPP and other Side B chemicals using the generic formulation s from high

- and low

- pressure foams and foams sprayed in the NI ST NZERTF [ 24 ]

. Eventually, these data and methods will aid in determining the compounds that may cause health effects in consumers and the factors that may cause elevated releases of these compounds [ 25 ] . EPA is evaluating approaches to identifying e m issions from MDI through micro

small

- , and full

- scale chambers to characterize emissions over time
, for up to several hundred hours post

- application of SPF. Continued research into MDI emission will hopefully predict potential exposures in the real environ ment [ 22 ]

. Industry Reviews

EPA and other F ederal P artners have also engaged in SPF industry conferences and provided courtesy review s on CPI’s and the Spray Polyurethane Foam Alliance’s (SPFA) fact sheets, training materials, websites, and original re search.

CONCLUS ION S

The F ederal P artner ’ s workgroup on SPF represents a model for understanding both worker and consumer exposures to a complex set of chemicals used in the application of SPF . The coordination between the federal agencies and industry i s exemplified in the recent ASTM D22.05 (Committee on Indoor Air ) symposium and in the International Isocyanate conference. The continuing efforts made by industry to understand worker exposure should be a model on how other chemical industries ’ exposure a ssessments should be conducted. However, without the continued presence of the federal agencies investigating exposures and requesting information from industry
, this type of collaboration would not have been possible. Transparency and continued discuss ion s with the federal agencies and industry is of the utmost importance to protect workers and consumers from the chemicals in SPF

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A CKNOWLEDGEMENTS We would like to thank the Environmental Protection Agency and the Consumer Product Safety Commission for the support of this work and Carol Hetfield of the EPA
, Robert Streicher of NIOSH
, Michael Babich of CPSC, Dustin Poppendieck of NIST
, and Janet Carter and Sven Rundman of OSHA for their review and expertise. We would also like to thank Andrea Pf

a h les

- Hutchens, Charles Bevington, Kristie Eg l s a e r, Doug Anderson, and Mary Cush mac (retired) of the EPA for their continued commitment to the F ederal Partners Work group, as well as Lynn Wilder of ATSDR, Kathy Ernst (retired) and Dan Almaguer of NIOSH, Dr. Dhi miter Bello of the University of Massachusetts Lowell, and Dr. Carrie Redlich of Yale University

.BIOGRAPHIES

Katherine Sleasman

Kathe rine Sleasman works on policy issues related to a variety of chemicals including isocyanates, methylene chloride, trichloroethylene, and perfluorinated chemicals as well as substantial risk information under the Toxic Substance Control Act Section 8(e). Sh e received her B.A. in Environmental Studies from the George Washington University and her M.S. in Environmental Studies from Florida International University in Miami. Her graduate thesis work focused on water quality management in the Florida Keys and wa s published in Ocean and Coastal Management and the Water Policy journal. Prior to joining the Office of Pollution Prevention and Toxics, she was an Oak Ridge Institute for Science and Education fellow at EPA’s Office of Wastewater Management.

Melanie Bi ggs , Ph.D

Melanie Biggs works on chemical

- related issues for various consumer products. She received her B.S. in Bioengineering from Western New England University, her M.S. in Toxicology from Northeastern University, and her Ph.D in Toxicology from th e University of North Carolina. Her graduate thesis work focused on the mechanisms of obesity with respect to the epidermal growth factor and a high

- fat diet

.



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