Identification of Flame Retardants in Polyurethane Foam ...

[Pages:27]Submitted to Environmental Science & Technology

Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products

Journal: Environmental Science & Technology

Manuscript ID: es-2011-007462.R1

Manuscript Type: Article

Date Submitted by the Author:

n/a

Complete List of Authors:

Stapleton, Heather; Duke University, Nicholas School of the Environment Klosterhaus, Susan; San Francisco Estuary Institute Keller, Alex; Duke University, Nicholas School of the Environment Ferguson, Lee; Duke University, Dept. of Civil & Environmental Engineering van Bergen, Saskia; East Bay Municipal Utility District Cooper, Ellen; Duke University, Nicholas School of the Environment Webster, Thomas; Boston University School of Public Health, Environmental Health Blum, Arlene; UC Berkeley

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Identification of Flame Retardants in Polyurethane Foam Collected

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from Baby Products

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4 Heather M. Stapleton 1, Susan Klosterhaus 2, Alex Keller 1, P. Lee Ferguson1, Saskia van

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5 Bergen3, Ellen Cooper 1, Thomas F. Webster4 and Arlene Blum 5 6

11 7 1- Nicholas School of the Environment, Duke University, Durham, NC, USA;

12 8 2- San Francisco Estuary Institute, Oakland, CA, USA;

13 9 3- East Bay Municipal Utility District, Oakland, CA, USA;

14 10 4-Department of Environmental Health, Boston University School of Public Health, Boston, MA,

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11 USA;

17 12 5- Department of Chemistry, University of California, and Green Science Policy Institute,

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20 15 *corresponding author: heather.stapleton@duke.edu

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16 17 Key Words: Flame Retardants, Polyurethane Foam, XRF, PBDEs, TDCPP, Firemaster

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26 20 ABSTRACT

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With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in

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31 23 polyurethane foam to meet flammability standards. However, insufficient information is

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33 24 available on the identity of the flame retardants currently in use. Baby products containing

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25 polyurethane foam must meet California state furniture flammability standards, which likely

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38 26 affects use of flame retardants in baby products throughout the U.S. However, it is unclear which

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40 27 products contain flame retardants, and at what concentrations. In this study we surveyed baby

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43 28 products containing polyurethane foam to investigate how often flame retardants were used in

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45 29 these products. Information on when the products were purchased and whether they contained a

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30 label indicating that the product meets requirements for a California flammability standard were

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50 31 recorded. When possible, we identified the flame retardants being used, and their concentrations

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52 32 in the foam. Foam samples collected from 101 commonly used baby products were analyzed.

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33 Eighty samples contained an identifiable flame retardant additive and all but one of these was

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57 34 either chlorinated or brominated. The most common flame retardant detected was tris (1,3-

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35 dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components

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6 36 typically found in the Firemaster?550 commercial mixture (detection frequency 17%). Five

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8 37 samples contained PBDE congeners commonly associated with PentaBDE, suggesting products

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38 with PentaBDE are still in-use. Two chlorinated organophosphate flame retardants not

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13 39 previously documented in the environment were also identified, one of which is commercially

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15 40 sold as V6 (detection frequency 15%) and contains tris (2-chloroethyl) phosphate (TCEP) as an

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41 impurity. As an addition to this study, we used a portable x-ray fluorescence (XRF) analyzer to

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20 42 estimate the bromine and chlorine content of the foam and investigate whether XRF is a useful

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22 43 method for predicting the presence of halogenated flame retardant additives in these products. A

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25 44 significant correlation was observed for bromine; however, there was no significant relationship

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27 45 observed for chlorine. To the authors knowledge, this is the first study to report on flame

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46 retardants in baby products. In addition, we have identified two chlorinated OPFRs not

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32 47 previously documented in the environment or in consumer products. Based on exposure

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34 48 estimates conducted by the Consumer Product Safety Commission (CPSC), we predict that

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49 infants may receive greater exposure to TDCPP from these products compared to the average

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39 50 child or adult from upholstered furniture, all of which are higher than acceptable daily intake

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41 51 levels of TDCPP set by the CPSC. Future studies are therefore warranted to specifically measure

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52 infants exposure to these flame retardants from intimate contact with these products, and to

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46 53 determine if there are any associated health concerns.

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51 55 INTRODUCTION

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Prior to 2004, PentaBDE was one of the most common flame retardant mixtures added to

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57 58 polyurethane foam in furniture and other consumer products, particularly in the US. Because of

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59 concerns regarding the persistence, bioaccumulation, and potential toxicity of the

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6 60 polybrominated diphenyl ethers (PBDE) present in this commercial mixture, California passed

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8 61 legislation banning its use in 2003. Eight other states and the European Union (EU) followed

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62 with similar bans and the sole U.S. manufacturer, Great Lakes Chemical (now Chemtura),

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13 63 voluntarily phased out production in 2004 (1-2). Alternative chemical flame retardants have

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15 64 since been used and identified as PentaBDE replacements in polyurethane foam (3-4). However,

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65 basic information on these alternative flame retardants, such as chemical identity, specific

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20 66 product applications, and volumes used, are typically not available, significantly restricting

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22 67 human and environmental health evaluations. Many of the chemical ingredients in flame

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25 68 retardant mixtures are proprietary, and are not disclosed by the chemical manufacturers, even to

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27 69 manufacturers using these chemicals in their final end products (e.g. furniture).

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The flammability standard primarily driving the use of flame retardant chemicals in

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32 71 polyurethane foam in the US is Technical Bulletin 117 (TB117), promulgated by the California

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34 72 Bureau of Electronic and Appliance Repair, Home Furnishings and Thermal Insulation. TB117

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73 requires that polyurethane foam in upholstered furniture sold in the State of California withstand

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39 74 exposure to a small open flame for 12 seconds (5). Though the standard does not specifically

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41 75 require the addition of flame retardant chemicals to the foam, polyurethane foam manufacturers

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76 typically use chemical additives as an efficient method for meeting the TB 117 performance

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46 77 criteria (6). Throughout the 1980s and 1990s, PentaBDE was used often in the US to comply

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48 78 with TB117. Numerous studies have since documented widespread contamination of the PBDE

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51 79 congeners found in the PentaBDE mixture in both humans and wildlife (7-8). PBDEs have also

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53 80 recently been identified in children's toys (9). Despite the fact that compliance with TB117 is

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81 only required for residential upholstered furniture sold in the State of California, a significant

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82 fraction of products sold elsewhere in the US also complies with TB117, and therefore also

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6 83 contains flame retardant additives.

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It is less well known that some baby products are considered juvenile furniture, and that

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85 the polyurethane foam used in baby products must also comply with TB117. However, the

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13 86 extent of baby product compliance with TB117 and whether or not the types of chemicals added

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15 87 to the polyurethane foam are similar to those in non-juvenile furniture is unknown. Flame

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88 retardant additives can escape from products over time, accumulate in dust, and are a primary

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20 89 route of exposure to humans (10-13). Exposure to children is a particular concern due to their

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22 90 frequent hand to mouth behavior and higher contact with floors. Exposure to chemical additives

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25 91 in baby products is of even greater concern for infants, who are in intimate contact with these

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27 92 products for long periods of time, at very critical stages of their development. Knowledge of the

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93 types of chemicals in use and the products they are used in are essential first steps for evaluating

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32 94 the potential for human exposure and subsequent health effects. Structural identities are also

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34 95 needed to track the fate and transport of these chemicals in the environment.

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The objective of this study was to survey a large number of baby products that contain

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39 97 polyurethane foam to investigate whether flame retardant chemicals were present and the

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41 98 concentrations in the foam in order to understand whether they may be significant source of

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99 exposure, particularly for infants. To do this we analyzed foam samples from baby products

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46 100 purchased in the US, primarily targeting the most commonly used products that contain

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48 101 polyurethane foam. A secondary objective was to determine whether portable x-ray fluorescence

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51 102 (XRF) is a useful method for predicting the presence of bromine or chlorinated flame retardant

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53 103 additives in these products. In a previous study, XRF-measured bromine was highly correlated

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with gas chromatography-mass spectrometry (GC/MS)-measured bromine in a limited number of

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105 pieces of furniture foam and plastics from electronics (12). However, Allen et al. focused on

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6 106 estimating PBDE content, and it is not known whether XRF is a useful indicator of the presence

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8 107 of other brominated and chlorinated flame retardants. Portable XRF has potential for use as a less

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expensive screening tool for researchers studying potential sources of flame retardant chemicals,

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13 109 as well as concerned members of the public, interested in avoiding products containing flame

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15 110 retardant chemicals. Data generated from this study will be useful for informing general

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consumers and scientists about specific flame retardants in use to better understand their fate,

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20 112 exposure and potential health effects from using these chemicals in consumer products.

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MATERIALS AND METHODS

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Materials. Internal standards were purchased from Chiron (Trondheim, Norway) and

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28 117 Wellington Laboratories (Guelph, Ontario). PBDE calibration standards were purchased from

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31 118 AccuStandard (New Haven, CT), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and bis (2-

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33 119 ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) were purchased from Wellington Laboratories.

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35 120 tris (2-chloroethyl) phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCPP) and tris (1,3-

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38 121 dichloroisopropyl) phosphate (TDCPP) were purchased from Sigma-Aldrich (St. Louis, MI),

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40 122 Pfaltz & Bauer (Waterbury, CT), and ChemService (West Chester, PA), respectively. All

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solvents used throughout this study were HPLC grade.

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Sample Collection. Foam samples were solicited from volunteers via email distributions

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48 126 to colleagues and listservs based primarily in the United States. Requests were made for samples

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51 127 of polyurethane foam from baby products, with specific requests for samples of car seats,

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53 128 strollers, changing table pads, nursing pillows, portable crib mattresses, and infant sleep

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positioners. Individuals interested in participating in our study were asked to cut out a small

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130 piece of the foam (approximately 2 cm x 2cm), wrap the foam in aluminum foil, and enclose it in

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6 131 a resealable plastic bag. Participants were also asked to complete a brief survey to collect

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8 132 information on the type of product, year of purchase, manufacturer, and whether the product

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possessed a label indicating that it met the criteria for TB 117, or Technical Bulletins 116 (TB

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13 134 116) or 603 (TB603). These latter two California flammability standards regulate flammability

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15 135 in upholstered furniture and mattresses, respectively. The samples were logged into a database

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and then split into two pieces, one for chemical analysis by mass spectrometry and one for

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20 137 elemental analysis using a portable XRF analyzer. Each analysis was conducted blind.

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Sample Analysis by Mass Spectrometry. All foam samples were first screened for flame

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27 140 retardant additives. Briefly, small pieces of foam (approximately 0.05 grams) were sonicated

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with 1 mL of dichloromethane (DCM) in a test tube for 15 minutes. The DCM extract was

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32 142 syringe-filtered to remove particles and then transferred to an autosampler vial for analysis by

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34 143 GC/MS. All extracts were analyzed in full scan mode using both electron ionization (GC/EI-MS)

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and electron capture negative chemical ionization (GC/ECNI-MS). Pressurized temperature

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39 145 vaporization injection was employed in the GC. GC/MS method details can be found in (3). All

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41 146 significant peaks observed in the total ion chromatograms were compared to a mass spectral

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database (NIST, 2005) and to authentic standards when available.

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If a previously identified flame retardant chemical was detected during the initial

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48 149 screening, a second analysis of the foam sample, using a separate piece of the foam, was

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51 150 conducted for quantitation using accelerated solvent extraction. Our methods for extracting and

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53 151 measuring flame retardants in foam are reported in Stapleton et al. [3]. A five point calibration

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curve was established for all analytes with concentrations ranging from 20 ng/mL to 2 ?g/mL.

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153 PBDEs were quantified by GC/ECNI-MS by monitoring bromide ions (m/z 79 and 81) and TBB

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6 154 and TBPH were monitored by molecular fragments m/z 357/471 and 463/515, respectively.

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8 155 TCEP, TCPP, and TDCPP were quantified by GC/EI-MS by monitoring m/z 249/251, 277/201,

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and 381/383, respectively.

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Because GC/MS analysis of foam samples suggested the presence of additional flame

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15 158 retardants that may have been thermally labile (decomposing partially in the injection port of the

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GC) or nonvolatile, all sample extracts were further analyzed by HPLC-high resolution mass

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20 160 spectrometry to determine if additional relevant compounds were present, which were not

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22 161 detected by GC/MS. HPLC-high resolution mass spectrometry (HPLC/HRMS) analyses were

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25 162 conducted using a LTQ-Orbitrap Velos tandem mass spectrometer (ThermoFisher Scientific,

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27 163 Bremen, Germany) with a Thermo Fisher Scientific Accela series UPLC system. Sample

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30 164 extracts (25 ?L) were separated on a Hypersil Gold 50 x 2.1-mm C18 column with 1.9 m

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33 165 particles (ThermoFisher Scientific) using a flow rate of 0.4 mL/min and a linear gradient from

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25 to 95% methanol/water in 9 minutes, followed by a 1-min hold at 95% methanol before

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38 167 returning to initial conditions for 2-mins. Sample extracts were analyzed using both positive

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40 168 polarity electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI)

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modes. Prior to analysis, mass calibration was performed daily by direct infusion of a calibration

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45 170 mixture prepared according to the instrument manufacturer's instructions. Mass spectral

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47 171 acquisition was programmed into five scan events running concurrently throughout the

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chromatographic separation. The first scan event was programmed to acquire full-scan (250-

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52 173 2000 m/z), high-resolution (R=60,000) orbitrap MS data with external mass calibration (< 2 ppm

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54 174 accuracy). The subsequent four scan events were low-resolution data-dependent MS/MS

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