Astm stp 1589 2017

Selected Technical Papers STP1589 Editors: John Sebroski and Mark Mason Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation ASTM STOCK #STP1589 DOI: 10.1520/STP1589-EB ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959 Printed in the U.S.A Library of Congress Cataloging-in-Publication Data Names: Sebroski, John, editor | Mason, Mark 1947-, editor Title: Developing consensus standards for measuring chemical emissions from spray polyurethane foam (SPF) insulation / editors: John Sebroski, Mark Mason Description: West Conshohocken, PA : ASTM International, [2016] | Series: Selected technical papers ; STP 1589 | “ASTM Stock #STP1589.” | Includes bibliographical references Identifiers: LCCN 2016046094 (print) | LCCN 2016046208 (ebook) | ISBN 9780803176232 | ISBN 9780803176249 (ebook) Subjects: LCSH: Insulating materials–Standards–United States | Insulation (Heat) Standards United States | Polyurethanes–Environmental aspects | Aerosols Environmental aspects Classification: LCC TH1715 D4115 2016 (print) | LCC TH1715 (ebook) | DDC 691/.95 dc23 LC record available at https://lccn.loc.gov/2016046094 Copyright © 2017 ASTM INTERNATIONAL, West Conshohocken, PA All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by ASTM International provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/ The Society is not responsible, as a body, for the statements and opinions expressed in this publication ASTM International does not endorse any products represented in this publication Peer Review Policy Each paper published in this volume was evaluated by two peer reviewers and at least one editor The authors addressed all of the reviewers’ comments to the satisfaction of both the technical editor(s) and the ASTM International Committee on Publications The quality of the papers in this publication reflects not only the obvious efforts of the authors and the technical editor(s), but also the work of the peer reviewers In keeping with long-standing publication practices, ASTM International maintains the anonymity of the peer reviewers The ASTM International Committee on Publications acknowledges with appreciation their dedication and contribution of time and effort on behalf of ASTM International Citation of Papers When citing papers from this publication, the appropriate citation includes the paper authors, “paper title,” STP title, STP number, book editor(s), ASTM International, West Conshohocken, PA, year, page range, paper doi, listed in the footnote of the paper A citation is provided on page one of each paper Printed in Bay Shore, NY February, 2017 Foreword THIS COMPILATION OF Selected Technical Papers, STP1589, Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation, contains peer-reviewed papers that were presented at a symposium held April 30–May 1, 2015, in Anaheim, California, USA The workshop was sponsored by ASTM International Committee D22 on Air Quality and Subcommittee D22.05 on Indoor Air Symposium Chairpersons and STP Editors: John Sebroski Covestro LLC Pittsburgh, PA, USA Mark Mason US Environmental Protection Agency Research Triangle Park, NC, USA Contents vii Overview Evaluation of Micro-Scale Chambers for Measuring Chemical Emissions from Spray Polyurethane Foam Insulation John Sebroski, Jason W Miller, Carl P Thompson, and Elizabeth Roeske Measurement of Chemical Emissions from Spray Polyurethane Foam Insulation Using an Automated Micro-Scale Chamber System Yunyun Nie, Eike Kleine-Benne, and Kurt Thaxton 27 VOC Analysis of Commercially Available Spray Foam Products J Paul Duffy and Richard Wood 43 Flame Retardant Emissions from Spray Polyurethane Foam Insulation Dustin Poppendieck, Matthew Schlegel, Angelica Connor, and Adam Blickley 57 Glass Chamber Method for Screening of 4,4'- MDI and TCPP Emissions from Foam Joint Sealant Doyun Won, Angelika Zidek, Gang Nong, and Ewa Lusztyk 77 Prioritizing Chemical Emissions from Closed-Cell Spray Polyurethane Foam: Utilizing Micro-Scale Chamber Emission Factors and Field Measurement Data Scott Ecoff, Shen Tian, and John Sebroski 98 Computer Simulation of Peak Temperatures in Spray Polyurethane Foam Used in Residential Insulation Applications Richard S Duncan 119 Assessment and Remediation of Misapplied Spray Polyurethane Foam Ed Light Estimating Re-Entry Times for Trade Workers Following the Application of Three Generic Spray Polyurethane Foam Formulations Richard Wood v 138 148 Predicting TCPP Emissions and Airborne Concentrations from Spray Polyurethane Foam Using USEPA i-SVOC Software: Parameter Estimation and Result Interpretation Shen Tian, John Sebroski, and Scott Ecoff A Modeling Approach for Quantifying Exposures from Emissions of Spray Polyurethane Foam Insulation in Indoor Environments Charles Bevington, Zhishi Guo, Tao Hong, Heidi Hubbard, Eva Wong, Katherine Sleasman, and Carol Hetfield Investigating Sampling and Analytical Techniques to Understand Emission Characteristics from Spray Polyurethane Foam Insulation and Data Needs Katherine Sleasman, Carol Hetfield, and Melanie Biggs VOC Emissions from Spray Foam Insulation Under Different Application Conditions Doyun Won, Joan Wong, Gang Nong, and Wenping Yang vi 167 199 228 278 Overview The Symposium on Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation was held on April 30–May 1, 2015 Sponsored by ASTM Committee D22 on Air Quality, the symposium was held in Anaheim, CA, in conjunction with the standards development meetings of the Committee ASTM D22.05 is developing tools to assist decision makers in answering fundamental questions, such as: What is emitted from SPF, how long the emissions persist, and how does ventilation impact concentrations and potential exposures? How can we model these processes to address the multiplicity of products, applications, and environmental conditions that may impact exposure to emissions over the life cycle of the material? These are complex and interrelated questions that have challenged the indoor environments research community for many years Objectives of Symposium SPF insulation is manufactured on-site by mixing and spraying chemicals that react to form an effective insulating material Standardized methods are needed to assess the potential impacts of SPF insulation products on indoor air quality, establish re-entry times for trade workers or ­re-occupancy times for building occupants after product installation and to evaluate post-occupancy ventilation The objective of the symposium was to provide a forum for SPF manufacturers, regulatory agencies, indoor air quality professionals, testing labs, air quality consultants, instrument vendors and other stakeholders to exchange information After a series of presentations on the current status of measuring emissions from SPF insulation, participants discussed paths forward for research, method development and development of standards The chairs of the symposium distributed a broad call for papers on the f­ ollowing topics, designed to represent the scope of complex challenges that diverse stakeholders, including industry and government, must address regarding the application and use of SPF insulation products: • Research and method development for measuring potential SPF emissions of semi-volatile and volatile organic compounds used in the formulation (e.g., isocyanates, blowing agents, amine catalysts and flame retardants) and from potential reaction or byproducts; • Federal and other governmental agencies’ regulatory approaches and supporting investigation, assessment and research needs; • Modeling, scaling up from lab to large scale chambers or buildings;  vii • International perspective on regulation and testing of SPF insulation emissions;  • Industry perspective/needs and product stewardship activities;  • Field investigations or large-scale chamber/spray booth studies to evaluate emissions or ventilation rates; and • Applying the knowledge from product emissions data/research to practice (e.g., stewardship commitment, green building practices, codes for residential ventilation and global leadership) The collaboration and exchange of information during the symposium and the corresponding research papers will support the development of standards at ASTM D22.05 on Indoor Air for measuring emissions from SPF New standards are being developed to estimate the emissions of volatile and semi-volatile organic compounds (e.g., blowing agents, catalysts, flame retardants, byproducts) with micro- and largescale chambers Analytical methods must be developed to measure emissions from the chambers Specialized chambers must be evaluated for measuring isocyanate emissions such as methylene diphenyl diisocyanate (MDI) to avoid adhesion to the chamber’s surfaces The data generated from the new ASTM standards may be useful as input parameters in computer simulation modelling software to help manufacturers and distributors, researchers, and government agencies assess exposure potential and control mechanisms for SPF products In the following paragraphs, the symposium co-chairs summarize key presentations, findings, and knowledge gaps and identify new standard development activities that have been introduced in ASTM D22.05 as outcomes of the symposium Selected Technical Papers with Excerpts from Abstracts Several topics are covered in the selected technical papers (STP) resulting from the symposium including: field investigation studies, emissions measured in varioussized test chambers, emissions from misapplied material, computer simulation modelling of emissions and peak SPF temperatures in residential homes According to the paper “Investigating Sampling and Analytical Techniques to Understand Emission Characteristics from Spray Polyurethane Foam Insulation and Data Needs,” reliable and validated emission test methods and sampling, and analytical protocols are needed to understand the variables that affect emissions and curing in order to develop and assess residential exposure scenarios The paper “Evaluation of Micro-Scale Chambers for Measuring Chemical Emissions from Spray Polyurethane Foam Insulation” evaluates the use of micro-scale chambers for measuring emissions and compares the results with conventional smallscale chambers The authors also investigated the effect of the chamber’s temperature and trimming samples prior to testing Automating the micro-scale ­chamber testing was demonstrated in the paper “Measurement of Chemical Emissions from Spray Polyurethane Foam Insulation Using an Automated Micro-Scale Chamber System.” An automated dynamic headspace system was used for on-line, fully automated viii micro-scale chamber measurements of SPF to evaluate sampling time, volume and temperature The paper “Prioritizing Chemical Emissions from Closed-Cell Spray Polyurethane Foam: Utilizing Micro-Scale Chamber Emission Factors and Field Measurement Data” compares emission factors from the m ­ icro-scale chambers in conjunction with a screening model to emissions measured in a residential home after application of SPF insulation The paper “Flame Retardant Emissions from Spray Polyurethane Foam Insulation” evaluates emissions of a commonly used flame retardant in SPF, tris (1-chloro2-propyl) phosphate (TCPP), with micro-scale chambers and a full scale Net Zero Energy Residential Test Facility The authors measured emissions in the test house without the installation of furniture, carpeting, or other household goods to determine if SPF in the facility was the primary source of the airborne concentrations of TCPP This flame retardant was also investigated in the paper “Glass Chamber Method for Screening of MDI and TCPP Emissions from Foam Joint Sealant.” The goal of this study was to develop a glass chamber method to examine the emissions of MDI and TCPP, which were measured during a 24-hour chamber test in a 3-L chamber There is a great need to determine when it is safe for trade workers to re-enter a work area where SPF was recently applied during retrofit or new construction Emissions from three generic SPF formulations were evaluated in a room-size chamber at ventilation rates ranging from to 10 air changes per hour in the paper “Estimating Re-Entry Times for Trade Workers Following the Application of Three Generic Spray Polyurethane Foam Formulations.” Chemicals selected for evaluation were MDI, amine catalysts, blowing agent and flame retardant that were used in the formulations The room-size chamber test was also utilized to evaluate commercial products in the paper “VOC Analysis of Commercially Available Spray Foam Products.” The study was aimed at determining if worker reentry times could be reduced from the industry practice of 24 hours if specific rates of workplace ventilation were employed According to the paper “Assessment and Remediation of Misapplied Spray Polyurethane Foam,” the misapplication of SPF may result in occupant complaints associated with persistent odor, and that SPF installed in homes may fail to cure and perform as anticipated when the contractor does not follow the distributors specified pre-application and installation procedures This paper discusses strategies for resolving odor complaints and suggests an assessment and mitigation protocol for field use Emissions from misapplied SPF are also investigated in “VOC Emissions from Spray Foam Insulation under Different Application Conditions.” The researchers compare chemical emissions from SPF insulation applied in four different ways in an attempt to simulate normal and abnormal applications Application temperature and A to B-side ratios are investigated to determine the effect of emissions To begin to understand exposure to emissions from SPF and to identify and characterize uncertainty in assessing chemical exposures, a proof-of-concept multizone indoor model to estimate indoor air concentrations of chemicals is described ix SLEASMAN ET AL., DOI: 10.1520/STP158920150037 [124] EPA, “MDI Action Plan Docket,” http://www.regulations.gov/#!docketDetail;D=EPA-HQOPPT-2011-0182 (accessed August 7, 2015) [125] Saskatchewan Research Council Building Performance Unit, “V.O.C Emissions Profiling of a Polyurethane Foam Sample,” http://www.regulations.gov/#!documentDetail; D=EPA-HQ-OPPT-2011-0182-0068 (accessed February 24, 2015) [126] Icynene, http://www.regulations.gov/#!documentDetail;D=EPA-HQ-OPPT-2011-01820065 (accessed February 24, 2015) [127] DOE, “Building Energy Codes Program,” (accessed December 29, 2015) [128] DOE, “Insulation,” http://energy.gov/public-services/homes/home-weatherization/ insulation (accessed August 7, 2015) [129] DOE, “Insulation Materials,” http://energy.gov/energysaver/articles/insulation-materials (accessed August 7, 2015) [130] EPA, “Energy Star Qualified Homes Building Science Introduction,” https://www.energystar gov/ia/partners/bldrs_lenders_raters/downloads/ENERGY_STAR_V3_Building_Science pdf (accessed December 29, 2014) [131] EPA, “An Introduction to Indoor Air Quality,” http://www.epa.gov/iaq/ia-intro.html# Causes (accessed January 20, 2015) [132] Garrett, D., “Proper Design of HVAC Systems for Spray Foam Homes,” http://www.icynene com/sites/default/files/US%20content%20uploads/builders/ProperDesignHVACSystems pdf (accessed February 27, 2015) [133] EPA, “Remodeling Your Home? Have You Considered Indoor Air Quality?” http://www epa.gov/iaq/homes/hip-ventilation.html (accessed March 25, 2015) [134] IECC, “Residential Provisions of the 2012 International Energy Conservation Code,” http://www.energycodes.gov/sites/default/files/becu/2012iecc_residential_BECU.pdf (accessed February 24, 2015) [135] EPA, “Healthy Indoor Environment Protocols for Energy Upgrades,” http://www.epa gov/iaq/pdfs/epa_retrofit_protocols.pdf (accessed February 24, 2015) 277 278 DEVELOPING CONSENSUS STANDARDS FOR MEASURING CHEMICAL EMISSIONS STP 1589, 2017 / available online at www.astm.org / doi: 10.1520/STP158920150042 Doyun Won,1 Joan Wong,2 Gang Nong,1 and Wenping Yang1 VOC Emissions from Spray Foam Insulation Under Different Application Conditions Citation Won, D., Wong, J., Nong, G., and Yang, W., “VOC Emissions from Spray Foam Insulation Under Different Application Conditions,” Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation, ASTM STP1589, J Sebroski and M Mason, Eds., ASTM International, West Conshohocken, PA, 2017, pp 278–290, http://dx.doi.org/ 10.1520/STP1589201500423 ABSTRACT Spray polyurethane foam (SPF) insulation has been reported to emit hazardous compounds if not applied correctly Because two-component low-pressure spray foam insulation is more readily available for a do-it-yourself project in homes, the importance of optimal application is getting attention We compared chemical emissions from spray foam insulations applied in four different ways in an attempt to simulate normal and abnormal applications The normal application (SPF1c) involved adhering to the manufacturer’s application instructions and assumed identical amounts of Components A and B (1 : 1) and a final foam thickness of in in two passes applied at room temperature (22–23 C) The Component A opening was reduced to a quarter turn in attempt to achieve a 0.25 : ratio with the intention of generating a nonoptimal ratio of two components in the next application (SPF1d) SPF1e and SPF1f were applied at 16 and 5 C, respectively, which are suboptimal compared to the recommended application temperatures of 21 to 32 C After application, the specimens were tested for days in 50-L chambers at 23 C, 50 % relative humidity, and air change per hour In general, the emission factors were higher if the foam was Manuscript received May 15, 2015; accepted for publication August 1, 2016 National Research Council Canada, Intelligent Building Operations, 1200 Montreal Rd., Ottawa, ON K1A 0R6, Canada Health Canada, Water and Air Quality Bureau, Indoor Air Contaminants Assessment, 269 Laurier Ave., West, Ottawa, ON K1A 0K9, Canada ASTM Symposium on Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation on April 30–May 1, 2015 in Anaheim, CA C 2017 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959 Copyright V WON ET AL., DOI: 10.1520/STP158920150042 applied below the manufacturer’s recommended application temperature More specifically, the emission factor was the highest when the foam was applied either at 5 C for the most volatile organic compounds (VOCs) or at 16 C for some VOCs, followed by SPF1d For example, the emission factor of triethyl phosphate increased by a factor of 2, 8, and 12 for SPF1d, SPF1e, and SPF1f, respectively This demonstrates that the VOC emissions can increase significantly when the spray foam is not applied according to the manufacturer’s application instructions Keywords spray foam insulation, chamber test, abnormal application, VOC emissions Introduction The demand for reducing energy consumption is growing for the building energy sector because it accounts for a significant portion of total energy both in the United States and around the world [1] Thermal insulation is one of the most effective and practical ways of achieving energy efficiency in homes [2] Among various insulation options, spray polyurethane foam (SPF) insulation has gained in popularity because of its performance and cost-effectiveness [3] Although the insulation is relatively inert when it is cured, there have been concerns about odor [4] and occupant health [3], possibly as a result of improperly cured SPF insulation We sought to determine VOC emissions from SPF specimens applied outside of manufacturer-recommended conditions that may reflect faulty applications We compared the chamber concentrations of selected VOCs from test specimens, which were applied either with strict adherence to the manufacturer’s instructions or with modifications to the application temperature and opening ratio of two components Methods PREPARATION OF TEST SPECIMENS A spray kit of a two-component low-pressure SPF product was purchased from a local home improvement store According to the manufacturer, the product can cover up to 200 board ft per kit and has an R value of 5.48 The recommended temperature ranges were 16 to 32 C for storage and 21 to 32 C for application The two-component spray foam insulation (SPF1) was applied into a galvanized metal specimen holder (approximately 0.2 by 0.254 by 0.05 m) lined with aluminium foil (Fig 1) in four different ways in an attempt to simulate normal and abnormal applications The resulting specimens had an uneven top surface (Fig 1) that was not cut in order to minimize any disturbance The application conditions can be found in Table SPF1c represents a normal application that follows the manufacturer’s application instructions and assumes an 279 280 STP 1589 On Developing Consensus Standards for Measuring Chemical Emissions FIG Test specimen contained in a metal box and tested in a 50-L chamber identical amount of Components A and B (1 : 1), 2-in foam thickness, and a twopass application at room temperature (22–23 C) There was an attempt to achieve a 0.25 : ratio of Components A and B with the intention of generating a nonoptimal ratio of two components to make SPF1d This was attempted by partially opening the Component A tank, i.e., a quarter opening compared to the full opening of the Component B tank SPF1e and SPF1f were applied at 16 and 5 C, respectively, which are suboptimal compared to the recommended application temperature of 21 to 32 C The 5 C application represented one of the extreme temperature cases Air temperature was monitored during the application using an Omega HH311 TABLE Application and test conditions Application Conditiona Test Condition Assumed A : B Ratio Temperature ( C) Weight (g)b Temperature ( C) Humidity (%) SPF1c 1:1 22.5 0.5 106.5 23.2 0.0 50 0.02 107.1 SPF1d 0.25 : 22.5 0.5 102.3 22.1 0.1 50 0.05 103.0 SPF1e : 1d 16 98.6 23.2 0.3 50 0.01 99.2 SPF1f : 1d 109.2 23.0 0.0 50 0.30 110.2 ID Weight (g)c a The relative humidity during the application was not controlled and was measured to be approximately 20 % b Weight of foam after application c Weight of foam after 4-day test d Although the two tanks were fully opened (1:1), the pressure of the two tanks could be different because of the pressure disturbance caused during the application of SPF1d (see the “Limitations and Recommendations” section for further discussion) WON ET AL., DOI: 10.1520/STP158920150042 humidity temperature monitor The humidity level during the application was measured to be approximately 20 % Two tanks of Components A and B were stored at a corresponding temperature for days before application CHAMBER TEST The specimen was introduced into a 50-L chamber within h after application with the intention of capturing early emissions The chamber was subjected to a 4-day test under standard conditions of 50 % relative humidity (RH), a temperature of 22 to 24 C, and air change per hour SPF1c and SPF1d were sprayed and tested on the same day (Week 1) Two electropolished stainless-steel 50-L chambers were operated simultaneously One chamber (Chamber 1) was enclosed in an environmental chamber, and the other chamber (Chamber 2) was placed in a room; both were maintained at a temperature of 23 1 C One week after the test of SPF1c and SPF1d, SPF1e was sprayed and tested in Chamber (Week 2) During the following week, the test for SPF1f was performed in Chamber (Week 3) Clean air for the chambers was supplied with an Aadco Model 737 Pure Air Generator The humidity of the supply air was maintained at a constant level of 50 0.3 % RH with the use of mass flow controllers to blend separate streams of Aadco air (one dry and one saturated by bubbling air through high-performance liquid chromatography [HPLC]-grade water) According to Table 1, the weight of a specimen was slightly increased after a test The increase of specimen weight typically occurs when the test RH is higher than the application RH; i.e., specimens seemed to absorb moisture because they were tested at 50 % RH after being applied at 20 % RH The pressure inside the chamber was maintained at approximately 60 Pa AIR SAMPLING AND CHEMICAL ANALYSIS During a 4-day test, air samples were collected at h, h, h, day, days, days, and days on sorbent tubes and 2,4-dinitrophenylhydrazine (DNPH) cartridges The two-layer sorbent tube (178 by by mm) packed with 160 mg TenaxV TA and 180 mg CarbographV 5TD was purchased from Camsco The DNPH cartridge was a Sep-Pak XPoSure from Waters The sampling volume was approximately to L at 100 to 200 mL/min for sorbent sampling and approximately 25 L at 250 mL/min for DNPH sampling Additional samples were taken on tubes packed with approximately 300 mg TenaxV TA for approximately 21 h at 100 mL/min, leading to a sampling volume of 90 to 130 L This was to check for the presence of semivolatile organic compounds (SVOCs) such as flame retardants The large sampling volume was required for SVOCs because the concentrations of SVOCs in the 50-L chambers at 23 C were expected to be low partly because of chamber sink effects Air samples collected on two-layer sorbent tubes were thermally desorbed and analyzed with a gas chromatography-mass spectrometry (GC-MS) system, including a Gerstel thermal desorption system (TDS) connected with an autosampler, an Agilent 6890 gas chromatograph equipped with a DB-624 capillary column (length, R R R 281 282 STP 1589 On Developing Consensus Standards for Measuring Chemical Emissions 30 m; inner diameter, 0.25 mm; thickness, 1.4 lm), and a 5973N Mass Selective Detector The desorbed analytes were injected with a programmable temperature vaporizer called a cooled injection system (CIS) that concentrated the sample before being injected onto the column of the gas chromatograph The GC system was operated in the TDS splitless/CIS split mode (split ratio of 20:1), and the MS system was operated in the full-scan mode (m/z ¼ 35–300) The TenaxV tubes were analyzed with a similar GC-MS system with a DB-5 capillary column (length, 30 m; inner diameter, 0.25 mm; thickness, 0.25 lm) and a mass scanning range of 35 to 800 The temperature profiles of the VOC and SVOC methods are provided in Table Carbonyl compounds were analyzed in accordance with ASTM D5197-09e1, Standard Test Method for Determination of Formaldehyde and Other Carbonyl Compounds in Air (Active Sampler Methodology) [5] Exposed DNPH cartridges were washed with acetonitrile, and the eluate was then analyzed by reverse-phase HPLC with ultraviolet (UV) detection at 360 nm The HPLC-UV system consisted of a Prostar 410 autosampler, Varian 9012 solvent delivery system with two Supelcosil LC-18 columns (length, 25 cm; inner diameter, 4.6 mm; thickness, lm) in a series maintained at 30 C, and Varian 9050 variable-wavelength UV-visible spectrophotometer A gradient of acetonitrile in water from 60 % to 100 % was used for separating carbonyl compounds Six-point calibration was performed with the use of three commercial liquid calibration mixtures (Supelco) for 120 VOCs and a commercial DNPH derivative mixture (Supelco) for carbonyl compounds The method detection limit (MDL), which was determined in accordance with guidance published by the US Environmental Protection Agency [6], ranged from 0.4 to 14.6 ng with an average of 3.7 ng for 120 VOCs and to 13 ng for carbonyl compounds Abundant compounds, which have a relatively large peak and are not included in the target VOC list, were quantified as a toluene equivalent The National Institute of Standards and R TABLE Temperature profiles of the GC/MS method (VOC and SVOC) VOC Desorption Initial temperature  60  C/min 60 C/min   Final temperature 300 C (holding min) 320 C (holding min) Initial temperature 90  C 20  C  Ramp GC 30  C 30 C Ramp Cooled injection system SVOC  12  C/s 12 C/s   Final temperature 300 C (holding min) 350 C (holding min) Initial temperature 10  C (holding min) 70  C (holding min) Ramp  C/min  20  C/min Middle temperature 230 C — Ramp 15  C/min — Final temperature 250  C (holding min) 320  C (holding min) WON ET AL., DOI: 10.1520/STP158920150042 Technology Mass Spectral Library (NIST98 version 1.7a) was used for the chemical identification of abundant compounds Background and blank samples were analyzed as a quality-control measure Background samples (TenaxV TA/CarbographV 5TD, TenaxV TA, and DNPH) were collected in an empty chamber before each test to verify chamber cleanliness In addition, blank samples were analyzed for each run of the GC-MS and HPLCUV systems In general, the background levels were higher than MDL for all three sampling methods Therefore, background levels were subtracted from chamber concentrations when emission factors were estimated (Eq 1) Because the blank levels were also higher than MDL for DNPH, the blank correction was made for carbonyl compounds collected on the DNPH cartridge The blank levels of sorbent tubes were typically lower than MDLs except for benzene Therefore, the blank correction was done for benzene only R R R Results and Discussion CHAMBER CONCENTRATIONS The chamber concentrations of VOCs emitted from SPF1c applied according to the manufacturer’s instructions are shown in Table VOCs are organized in three groups based on three sampling media The reported time corresponds to the midpoint of the sampling time Among the VOCs collected on the TenaxV/CarbographV, six were detected above MDLs The dominant VOC that was not on the target list was trans-1,2dichloroethene (TDCE), which is typically used as a blowing agent enhancer The concentration of TDCE was 6,339 lg/m3 at h and 2,282 lg/m3 at 96 h Other detected VOCs had lower concentrations than TDCE by to orders of magnitude For example, triethyl phosphate, which was likely to be used as a flame retardant, had a concentration of 17.2 lg/m3 at h and 11.4 lg/m3 at 96 h Hydrofluorocarbon blowing agents were not detected because of the standard practice of monitoring the mass starting at as a precaution to remove any solvent peak Table also shows two low-molecular-weight aldehydes (acetaldehyde and propanal) sampled on the DNPH cartridges Formaldehyde levels are not shown because they were below MDL Aldehydes are known to be formed from oxidative degradation of tertiary amine catalysts used in polyurethane foams [7] It is interesting to see there were no amine catalysts detected in in the TenaxV/CarbographV samples despite the presence of aldehydes This may be because of a low sampling volume or the presence of reactive catalysts that tend to be entrained in the polyurethane matrix [8] SVOCs collected on the TenaxV TA tubes are also summarized in Table The Tenax TA tubes for SVOC sampling did not reveal the presence of more chemicals in addition to those detected by VOC sampling One exception was tris(1-chloro-2propyl) phosphate (TCPP) (Table 3) TCPP was not detected by VOC sampling most likely because of the low sampling volume Although two siloxane compounds R R R R R 283 284 STP 1589 On Developing Consensus Standards for Measuring Chemical Emissions TABLE VOC and SVOC chamber concentrations from SPF1c Chamber Concentration by Tenax /Carbograph (lg/m3) R V Compound CAS # 0h R V 3h 6h 23.9 h 48 h 72 h 96 h 2-Ethyl-1-hexanol 104-76-7 0.6 0.7 0.6 0.4 0.5 0.5 Acetone 67-64-1 0.9 0.8 0.4 0.3 0.2 0.2 Texanol 25265-77-4 1.2 1.8 1.4 0.7 0.8 0.4 1,2-Dichloroethane 107-06-2 1.9 1.8 0.9 0.7 0.6 1,2-Dichloropropane 78-87-5 1.0 0.9 0.5 0.4 0.4 17.2 26.4 48.4 22.0 14.2 Triethyl phosphate 78-40-0 trans-1,2-Dichloroethenea 156-60-5 0.0 11.4 6338.9 5387.9 3819.6 2877.0 2511.6 2282.0 Chamber Concentration by DNPH Sampling (lg/m3) Acetaldehydeb 75-07-0 Propanalb 123-38-6 0h 4.1 h 7.1 h 25 h 49.1 h 73.1 h 0.6 4.4 3.3 1.9 1.2 1.0 97.1 h 1.2 14.0 10.1 5.1 3.0 2.1 1.5 Chamber Concentration by Tenax Sampling (lg/m3) R V Tris(1-chloro-2-propyl) 13674-84-5 0h 15.7 h 38.1 h 62.1 h 86.3 h 0.0 1.2 11.7 11.7 10.0 phosphatea a D5a 541-02-6 0.6 10.2 10.2 10.5 12.3 D6a 540-97-6 0.4 4.7 2.9 2.4 2.1 Abundant compound quantified as a toluene equivalent DNPH sampling b were detected in the VOC samples, they were not quantified because they were outside of the 120 target compounds Instead, they were quantified as a toluene equivalent in the SVOC sample It is not clear whether siloxane compounds are byproducts of the GC column bleed or siloxane surfactants used in the foam In general, the chamber concentrations decreased over time One exception was TCPP, for which the concentration increased from 15.6 to 38 h and was maintained at a relatively constant level afterward This was likely because TCPP belongs to a group of SVOCs The steady increase of a concentration in a chamber is one of the characteristics of SVOC emissions, likely because of slow emissions and substantial sink effects affected by low vapor pressure Similar observations were made in other tests (SPF1d, 1e, and 1f) Whereas dodecamethylcyclohexasiloxane (D6) showed a decreasing trend with time, decamethylcyclopentasiloxane (D5) had relatively constant emission factors over time No clear reason can be found to explain the difference in the decay patterns of D5 and D6 However, it may be speculated that the decreasing trend of D6 supports the proposition that it is a by-product of siloxane surfactants rather than the GC column bleed Further information is required to validate this assumption WON ET AL., DOI: 10.1520/STP158920150042 FIG Emission factors for acetone and Texanol COMPARISON OF EMISSION FACTORS The emission factors were calculated from the measured chamber concentrations normalized to the specimen weight (Eq 1) EFW ẳ 1; 000C  Cin ịQ=W (1) where: EFw ¼ emission factor normalized to specimen weight, ng/gh, C ¼ VOC concentration in the chamber, lg/m3, Cin ¼ VOC background concentration in the empty chamber, lg/m3, Q ¼ chamber flow rate, m3/h, W ¼ weight of a specimen, g, and 1,000 ¼ a conversion factor from lg to ng The emission factors normalized to the specimen weight are compared for acetone and Texanol in Fig 2, chlorinated compounds in Fig 3, aldehydes in Fig 4, phosphorous compounds in Fig 5, and siloxanes in Fig In general, the emission factors FIG Emission factors for chlorinated compounds 285 286 STP 1589 On Developing Consensus Standards for Measuring Chemical Emissions FIG Emission factors for aldehydes were the highest with the specimen applied at 5 C (SPF1f), followed by the specimen applied at 16 C (SPF1e), specimen SPF1d, and the specimen applied according to the manufacturer’s instructions (SPF1c) Exceptions were aldehydes and siloxanes For example, acetaldehyde (Fig 4a) showed the highest emission factor with the specimen applied at 16 C (SPF1e) Propanal (Fig 4b) also had the highest emission factor at 16 C (SPF1e) at the beginning However, the emission factors of propanal became similar for all specimens after 24 h Two siloxanes (D5 and D6) (Fig 6) had the highest emission factor at 16 C To obtain a quick overview of how much the emission rates were increased for suboptimal specimens, the emission factors from suboptimal applications were normalized to those of the normal application (SPF1c) The ratios were slightly different at each sampling time Table presents the ratios averaged for 48, 72, and 96 h; the ratios >1.5 or