flame retardant applications in residential furniture: results...
TRANSCRIPT
Heather M. Stapleton, Ph.D.Associate Professor of Environmental ChemistryNicholas School of the EnvironmentEmail: [email protected]
Ellen M. Cooper, Ph.D.Research ScientistNicholas School of the EnvironmentEmail: [email protected]
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