Heather M. Stapleton, Ph.D.Associate Professor of Environmental ChemistryNicholas School of the EnvironmentEmail: heather.stapleton@duke.edu

Ellen M. Cooper, Ph.D.Research ScientistNicholas School of the EnvironmentEmail: ellen.cooper@duke.edu

FlameRetardantApplicationsinResidentialFurniture:ResultsfromtheDukeSuperfund

FoamScreeningProject

Agenda1. Backgroundontheuseofflameretardantsin

furniture2. Describemotivationforthisproject3. Overviewofsamplesubmissionand

processing4. Discussionofdatacollectedtodate5. Discussiononexposureandpotentialhealth

effects6. Questions?

Why are there Flame Retardants (FRs) in Furniture?

• Due to concerns about fire, and furniture acting as an ignition source, the California Bureau of Home Furnishing and Thermal Insulation implemented Technical Bulletin 117 in 1972.

• Required filling material to withstand a 12-second open flame test

• Led to the use of high volumes of additive flame retardants in residential furniture

PentaBDE Flame Retardant Mixture• Anadditiveflameretardantmixtureappliedto

polyurethanefoaminfurniture

• 98%ofworldmarketdemandforPentaBDE wasinNorthAmerica,primarilytomeetCATB117

• StudiesdemonstratedthatPBDEswereubiquitouslydetectedinhumantissues;increasingconcentrationsdetectedinbioticandabioticsamples(Hites,2004)

• Concernaboutpersistence,bioaccumulationandpotentialtoxicityledtobanonuseinEuropeUnion(2002);voluntaryphase-outinUS(2005)

• Whatwouldbeusedasareplacement?

O2

3

45

2'3'

4'5'

6 6'

Polybrominated Diphenyl Ether (PBDE)

Brn n=1-10

Identifying Flame Retardants (FRs) Used to Meet California’s TB 117

• Previous research in our laboratory has focused on identifying FR chemical additives in polyurethane foam:• Baby Products (Stapleton et al. 2011)• Residential Sofas (Stapleton et al. 2012)

• The most common FRs identified in furniture are:• PBDEs associated with PentaBDE• Tris (1,3-dichloro-isopropyl) phosphate

(TDCPP)• Chemicals associated with Firemaster® 550

(FM 550)• Triphenyl phosphate (TPP) and isomers of

tris(4-isobutyl) phenyl phosphate • Tris (1-chloro-isopropyl) phosphate (TCPP)

SleepPositioners

1. How frequently are flame retardants used in other furniture items?

2. With addition of TDCPP to the California Proposition 65 list (“Prop 65”), will its use in furniture decrease?

3. How will use of flame retardants change in response to changes in TB 117? (i.e. TB 117-2013; changed from an open flame to smolder test)

NewQuestionsHaveBeenRaised

NewTB117Label

http://foam.pratt.duke.edu

• UniqueFRtestingservicelaunchedinFebruary2014

• IntendedtoscreenPUFsamplesandprovideinformationtothegeneralpublic

• SupportedbySuperfundResearchProgram

SubmittingaSample• WhattypeofproductisthePUFfrom?• Inwhatyearwasitpurchased?• Inwhatstatewasitpurchased?• DoesithaveaTB-117labelaffixedtotheproduct,andifso,whatversion?

• Inwhatcountrywasitmanufactured?

• SinceopeningtheprograminFebruary2014wehavenowreceivedmorethan1500samplesforscreening.

Howweprepareafoamsample

Throughouttheentireprocess,careistakentominimizecontamination,andcarryoverbetweensamples.

Glovesarewornforpersonalprotection,butalsotopreventcontamination.

Toolsarerinsedwithsolventbetweeneachsample,andtheworkspaceiskeptclean.

Remember:

Ourservice onlyanalyzespolyurethanefoam.Othermaterialssentin(e.g.,styrofoam)arenotanalyzed.

Sampleweightsarekeptconsistenttoensureconsistencyinanalysis.

Glassisusedbecausemostflameretardantsweanalyze“stick”toplastic.

Ultrasonic wavesfacilitatetheextractionoftheflameretardantchemicalsfromthefoam.

Remember,theseflameretardantsarejustaddedtothefoam,notincorporatedintothefoam’sstructure,sotheycomeouteasily.

Wedilutetheextractbecauseflameretardantsareaddedatveryhighlevelsinfoamthatcanoverwhelmourinstrument.

Thenwe:- Identify flameretardants(using authenticstandards)- Enterinformation intodatabase- TurnthingsovertoBryanforreporting…

Flame retardants included in screening

Flame retardants included in screening

Results Recently Published:

DOI:10.1021/acs.est.6b01602

Table 1. Description of foam samples received from project inception through June 2016. Category Total

products Products with FRa Products with no FR

Detected Sofas and loveseats 451 250 (28.4%) 201 (14.9%) Chairs 130 82 (15.9%) 48 (16.7%) Mattress pad 106 31 (19.4%) 75 (18.7%) Child car seat 98 72 (31.9%) 26 (54.0%) Mattress 71 22 (18.2%) 49 (16.3%) Other 59 25 (20.0%) 34 (17.6%) Other child products 49 21 (28.6%) 28 (28.6%) Rocking chairs and recliners 44 27 (22.2%) 17 (0%) Child mattress 36 13 (15.0%) 23 (22.0%) Pit cubes 39 33 (15.2%) 6 (50.0%) Pillows 32 9 (11.1%) 23 (21.7%) Other furniture 26 13 (23.0%) 13 (23.1%) Total 1141 598 (24.2%) 543 (19.2%) a Values in parenthesis are percentages of products purchased in California under each column header.

SampleDescriptions

Cooperetal.2016

ResultsThroughJune2016(DetectionindicatesFRis>1.0%byweight)

Cooperetal.2016

Chairsn=130

16 contained > 1 flame retardant

Mattress padsn=106

2 contained > 1 flame retardant

Rocking chairs and Reclinersn=44

5 contained > 1 flame retardant

Sofas and Love seatsn=451

23 contained > 1 flame retardant

Child mattressn=36

15contained > 1 flame retardant

Other child productsn=49

9 contained > 1 flame retardant

PentaBDE FM550 FM600 TCIPP TDCIPP TBPP V6 none detected

All samplesn=1141

90 contained > 1 flame retardant

Child car seat

15 contained > 1 flame retardant

n=9869

111

25

100

274

6018

543

3

26

49

4

261 1

4

3

5

21

23

111

14

11

28

41

47

821

113

313

201

914

7

14

3565

48

1

9

1

4

1231

17

3 814

9

6

1

75

FR detection frequency trends

Cooperetal.2016

14.8%

39.3%

21.9% 25.8%

0%

20%

40%

60%

80%

100%

1950-1999 2000-2004 2005-2013 2014-2016

Sofas and Loveseats

%ND

%FR

% fromCA

n = 81 n = 61 n = 187 n = 62

Perc

ent o

f Sam

ples

12.8%7.7%

19.0%

31.3%

0%

20%

40%

60%

80%

100%

1950-1999 2000-2004 2005-2013 2014-2016

Chairs, Rocking Chairs and Recliners

%ND

%FR

% fromCA

n = 39 n = 13 n = 79 n = 16

Perc

ent o

f Sam

ples

25.0%18.2% 21.1% 16.7%

0%

20%

40%

60%

80%

100%

1950-1999 2000-2004 2005-2013 2014-2016

Mattress pads

%ND

%FR

fromCA

n = 4 n = 11 n = 71 n = 15

Perc

ent o

f Sam

ples

32.1%

47.6%

0%

20%

40%

60%

80%

100%

1950-1999 2000-2004 2005-2013 2014-2016

Child Car Seats

%ND

%FR

% fromCA

n = 0 n = 0

n = 53 n = 42

Perc

ent o

f Sam

ples

ND: none detected; FR: FR detected

Changes in FR Use: Sofas and Loveseats pre/post 2005

• PentaBDE inveryfewsamplespurchased>2005• Useofalternateflameretardantsincrease>2005• TCIPPnot observed<2005

Cooperetal.2016

44% 41%

0% 4% 5%2%

44%

13% 17%

28%

0%10%20%30%40%50%60%70%80%90%

100%

PentaBDE TDCIPP TCIPP TBPP FM550

< 2005

>= 2005

% o

f Pro

duct

s C

onta

inin

g an

FR

47%

7%12%

20%11%

22% 17% 17%

0%10%20%30%40%50%60%70%80%90%

100%

TDCIPP TCIPP TBPP FM550

Sofas and Love Seats

< 2014

>= 2014

% o

f Pro

duct

s C

onta

inin

g an

FR

Changes in FR Use: pre/post 2014• Between 2000-2014, >70% of sofas

and loveseats were treated with FRs.Since 2014, less than 40% of sofas and loveseats are treated with FRs.

• Use varies with product type: noticeable shifts in products that fall under TB117

• TDCIPP clearly decreases >2014• TBPP and TCIPP use increases

>2014 in TB117 products• No TBPP in Car Seats

• Decrease in TDCIPP in products >2014 may also reflect TDCIPP addition to Prop 65

(FMVSS 302)

(TB117)

Cooperetal.2016

77%

29%

0% 4%

48% 52%

0% 5%0%

10%20%30%40%50%60%70%80%90%

100%

TDCIPP TCIPP TBPP FM550

Child Car Seats

< 2014>= 2014

% o

f Pro

duct

s C

onta

inin

g an

FR

ResultsfromFoamScreeningSuggest:• PentaBDE use(andthusexposure)hassignificantlydecreasedsince2005

• Useofalternateflameretardantshasincreased• TheuseofTDCIPPappearstobedecreasingsince2014;coincidingwithadditionofTDCIPPtoCAProp65list

• Overlasttwoyears,increasingdetectionofTCIPPandorganophosphatemixturesobserved

• Studiesonhealtheffectsofneworganophosphateflameretardantsarelimitedorlacking

TDCPP

§ TDCPP(e.g.Fryrol FR-2)wasusedasaFRinchildren’spajamasinthe1970s

§ ResearchpublishedinSciencesuggeststhatTDCPPanditsbrominatedanalogueweremutagenic(likelytocausecancer).(Goldetal1978;Blumetal1977)

§ StudiesconductedbytheNationalToxicologyProgramalsofoundIncreasedIncidenceoftumorsinratsexposedtoTDCPPover2years(NTP,2000)

§ SeveralrecenttoxicologystudieshavefoundthatexposuretoTDCPPinratsandfishhasledtosignificantchangesinthyroidregulation(Xuetal.2015;Wangetal.2015;Zhaoetal.2016)

§ Urinarymetabolitesdetectedinmorethan90%ofUSpopulation;levelssignificantlyhigherinchildrenrelativetoadults(Hoffmanetal.2015Buttetal.2016)

Cl

Cl

Cl Cl

Cl

ClO

OO

O

P

TCPP

§ StructurallysimilartoTDCPP

§ Inzebrafishstudies,itwasnotasacutelytoxicasTDCPP.Noimpactsonneurobehavioralassessments(Dishaw etal.2014)

§ Inastudywithchickenembryos,exposuretoTCPPresultedindelayeddevelopmentanddisruptionofthyroidendpoints(Farhart etal.2013)

§ ArodentcarcinogenicitystudyiscurrentlybeingconductedbytheNationalToxicologyProgram.

§ Urinarymetabolitesdetectedin100%ofsamplesrecentlytested(Buttetal.2016)

Cl

Cl

Cl

O

OO

O

PCH3

CH3

CH3

Firemaster 550

TBB

TBPHITPs

TPP

• FM550hasgainedmarketsharesincethephase-outofpentaBDE

• (Stapletonetal.,2012)

• HumanexposuretoFM550iswidespread(Hoffmanetal.,2014;Buttetal.,2014;Liuetal.,2015)

• ComponentsofFM550havebeendemonstratedtobepotentially

• Adipogenic• Endocrinedisrupting• Neuro- anddevelopmentally

toxic(Patisaul etal.,2013;Pillaietal.,2014;Belcheretal.,2014;Behl etal.,2015)

• FM550componentsareprioritizedforriskassessmentbytheU.S.EPA

LogKOW=4.7 LogKOW=7.7

LogKOW=12.0LogKOW=5.3– 9.1

ToxicityAssessmentsbyNTP(Behl etal.2015)

• AseriesofstudiesconductedbyresearchersattheNationalToxicologyProgramandtheUSEPAevaluatedtherelativetoxicitiesofnewflameretardants(FRs)comparedtoBDE-47(PentaBDE)

• SeveraloftheorganophosphateflameretardantsfoundinFiremaster 550(TPP,ITP),andthemixtureweidentifyas“TBPP”(BPDP)wereequallyormoretoxicthanBDE-47

• Relative“potency”ofseveralFRsbasedondevelopmentaltoxicity,developmentalneurotoxicity,andacutetoxicity:

• TPP,ITPandBPDPdisplayedgreateroverttoxicityinzebrafishcomparedtoBDE-47

• ITPandBPDPdisplayedgreaterimpactsonneuronalfiringratesinratneuronscomparedtoBDE-47

How Can one Reduce Exposure?

§ Morethan90%ofthepopulationhasdetectablelevelsoftheseFRsintheirbodies;levelsaregenerallyhigherinchildren.Toreduceexposure,onecantakethesesteps:§ Exchangefurnitureifeconomicallyfeasible§ Washhandsfrequently,particularlybeforeeating(Hoffmanetal.2014,

2015,Buttetal.2016)§ Vacuumandcleanhomemorefrequently§ Airpurifiershelpremoveparticlesfromtheindoorair,whichwillreduce

someexposures,butnotall.

§ Seeourwebsiteformoreinformation

§ http://foam.pratt.duke.edu/resources

OurNextSteps…1. WewillcontinuetoanalyzePUFforFRsforat

leastanotheryearwithourcurrentfunding.

2. Weareconsideringanalyzingtextilesinfuturestudies.

3. Wearecurrentlytryingtounderstandlinksbetweenuseofspecificchemicalsinconsumerproductsandexposure(whichproductscontributemosttoourexposure?)

QuestionsReceived:1. WherecanIhavemybloodtestedforflame

retardants?

2. CanyoutellmewhichmanufacturersarestillusingFRsinfurniture?

3. Whichflameretardantismosttoxic?

4. WherecanIpurchasefurniturewithoutFRs?

AcknowledgmentsCollaborators:Dr. Lee Ferguson (Duke University)Dr. Charlotte Clark (Duke University)Dr. Tom Webster (Boston University)

Thank you to all our participants!!!

Grant# P42ES010356

Research Technicians:Katie DavisEmina HodzicGretchen KroegerEileen ThorsosBryan LuukinenCatherine Kastleman