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Flame Retardant Transfers from U.S. Households (Dust and Laundry Wastewater) to the Aquatic Environment

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Levels of flame retardants in house dust and a transport pathway from homes to the outdoor environment were investigated in communities near the Columbia River in Washington state (WA). Residential house dust and laundry wastewater were collected from 20 homes in Vancouver and Longview, WA and analyzed for a suite of flame retardants to test the hypothesis that dust collecting on clothing and transferring to laundry water is a source of flame retardants to wastewater treatment plants (WWTPs) and subsequently to waterways. Influent and effluent from two WWTPs servicing these communities were also analyzed for flame retardants. A total of 21 compounds were detected in house dust, including polybrominated diphenyl ethers (PBDEs), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB or EH-TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), 1,2-bis(2,4,6,-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD or HBCDD), tetrabromobisphenol A (TBBPA), and three chlorinated organophosphate flame retardants (ClOPFRs), tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(2-chloroethyl)phosphate (TCEP). Levels ranged from 3.6 to 82,700 ng g(-1) (dry weight). Of the 21 compounds detected in dust, 18 were also detected in laundry wastewater. Levels ranged from 47.1 to 561,000 ng L(-1). ClOPFRs were present at the highest concentrations in both dust and laundry wastewater, making up 72% of total flame retardant mass in dust and 92% in laundry wastewater. Comparison of flame retardant levels in WWTP influents to estimates based on laundry wastewater levels indicated that laundry wastewater may be the primary source to these WWTPs. Mass loadings to the Columbia River from each treatment plant were by far the highest for the ClOPFRs and ranged up to 114 kg/yr for TCPP.
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Flame Retardant Transfers from U.S. Households (Dust and Laundry
Wastewater) to the Aquatic Environment
Erika D. Schreder*
,
and Mark J. La Guardia
Washington Toxics Coalition, 4649 Sunnyside Avenue N, Suite 540, Seattle, Washington 98103, United States
Department of Environmental & Aquatic Animal Health, Virginia Institute of Marine Science, College of William & Mary,
Gloucester Point, Virginia 23062, United States
*
SSupporting Information
ABSTRACT: Levels of ame retardants in house dust and a
transport pathway from homes to the outdoor environment
were investigated in communities near the Columbia River in
Washington state (WA). Residential house dust and laundry
wastewater were collected from 20 homes in Vancouver and
Longview, WA and analyzed for a suite of ame retardants to
test the hypothesis that dust collecting on clothing and
transferring to laundry water is a source of ame retardants to
wastewater treatment plants (WWTPs) and subsequently to
waterways. Inuent and euent from two WWTPs servicing
these communities were also analyzed for ame retardants. A
total of 21 compounds were detected in house dust, including
polybrominated diphenyl ethers (PBDEs), 2-ethylhexyl-2,3,4,5-
tetrabromobenzoate (TBB or EH-TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), 1,2-bis(2,4,6,-
tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD or
HBCDD), tetrabromobisphenol A (TBBPA), and three chlorinated organophosphate ame retardants (ClOPFRs), tris(1,3-
dichloro-2-propyl)phosphate (TDCPP or TDCIPP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(2-
chloroethyl)phosphate (TCEP). Levels ranged from 3.6 to 82,700 ng g1(dry weight). Of the 21 compounds detected in
dust, 18 were also detected in laundry wastewater. Levels ranged from 47.1 to 561,000 ng L1. ClOPFRs were present at the
highest concentrations in both dust and laundry wastewater, making up 72% of total ame retardant mass in dust and 92% in
laundry wastewater. Comparison of ame retardant levels in WWTP inuents to estimates based on laundry wastewater levels
indicated that laundry wastewater may be the primary source to these WWTPs. Mass loadings to the Columbia River from each
treatment plant were by far the highest for the ClOPFRs and ranged up to 114 kg/yr for TCPP.
INTRODUCTION
The global use of ame retardants (FRs) in consumer and
building products, including in polyurethane foam items such as
couch cushions, in plastics such as television housings, in
electronics, and in building materials including insulation, has
led to their accumulation throughout the environment.
13
With
the exception of known discharges from manufacturing,
recycling, and wastewater treatment, the mechanisms by
which FRs are transported from indoor to outdoor environ-
ments are poorly understood.
4,5
FRs have been detected in air,
water, sediments, surface lms, and tree bark, indicating that
once released from associated materials, they can enter the
environment through multiple pathways.
69
A recent report
detected a broad suite of 62 FRs in indoor dust, and several
reports have detected many of these compounds on surface
wipes, hands, hair, and in clothes dryer lint, indicating their
mobility within the indoor environment.
2,1012
Incidental
ingestion of dust is believed to be a signicant pathway for
human exposure to FRs. In addition to detections in humans,
including in breast milk, adipose tissue, and serum, a number of
FRs have been detected in shell- and nsh and marine
mammals including orcas, indicating their potential to
accumulate in the aquatic environment.
13,14
Some FRs have
been linked to toxic eects including cancer, hormone
disruption, neurotoxicity, and reproductive impacts.
3,15
Because of their heavy use in polyurethane foam as well as in
household plastics, polybrominated diphenyl ethers (PBDEs)
were the dominant FR analyzed in U.S. household dust until
recently.
1,16
Industry ended U.S. production of the penta
formulation of PBDEs at the end of 2004 and sales of the deca-
BDE formulation at the end of 2013.
17,18
Recent tests of foam-
containing products and of dust in U.S. homes indicate
increased use of chlorinated organophosphate ame retardants
(ClOPFRs) such as tris(1,3-dichloro-2-propyl)phosphate
(TDCPP) and tris(1-chloro-2-propyl)phosphate (TCPP), as
Received: May 14, 2014
Revised: July 11, 2014
Accepted: July 18, 2014
Article
pubs.acs.org/est
© XXXX American Chemical Society Adx.doi.org/10.1021/es502227h |Environ. Sci. Technol. XXXX, XXX, XXXXXX
well as components of the FR Firemaster 550 (Chemtura, PA,
USA): triphenyl phosphate (TPP), bis(2-ethylhexyl) 3,4,5,6-
tetrabromophthalate (TBPH), and 2-ethylhexyl-2,3,4,5-tetra-
bromobenzoate (TBB).
2,19
Other FRs known to be found
extensively in consumer and building products include
tetrabromobisphenol A (TBBPA), used in electronics, and
hexabromocyclododecane (HBCD), used primarily in insu-
lation and to a lesser extent on textiles.
20,21
Due to growing
environmental and human health concerns, the U.S. Environ-
mental Protection Agency (USEPA) is now evaluating these
and 13 other FRs under the Toxic Substances Control Act.
22
PBDEs were phased out largely because of their ability to
persist in the environment and build up in the food chain along
with evidence of toxicity.
23
In the Columbia River, USA and
Canada, PBDEs have been detected in the bodies and stomach
contents of juvenile salmon, with the highest concentrations in
more industrialized areas of the lower Columbia.
24
Some FRs
such as HBCD share PBDEscharacteristic as persistent
bioaccumulative compounds.
3
These hydrophobic compounds
partition preferentially to sewage sludge, with more than 90% of
PBDEs in wastewater treatment found in sludge.
25,26
Others,
such as ClOPFRs, are more hydrophilic and pass through
WWTPs, partitioning to euent rather than sludge.
15
A U.S.
Geological Survey study found two ClOPFRs (TCEP and
TDCPP) in euent from each of nine WWTPs discharging
into the Columbia River at levels ranging from 120 to 690 ng
L1.
27
No data have been published on levels of ClOPFRs in
Columbia River surface water. However, Kolpin et al. found
TCEP in 58% of 85 U.S. streams sampled in 1999 and 2000, at
a median level of 100 ng L1.
28
European studies have also
investigated ClOPFRs in surface water: TCEP, TDCPP, and
TCPP were detected in urban and rural surface waters in
Germany.
29,30
ClOPFRs have been detected in biota including
mollusks, sh, birds, and bird eggs.
15,31
This study tested the hypothesis that clothing, and the dust it
carries, creates a pathway for chemicals used in household
products to travel to waterways. In this pathway, chemicals such
as FRs escape from household products and accumulate in
house dust and on clothing. When that clothing is washed, the
FRs and/or particulate matter including FRs enter laundry
wastewater and make their way to wastewater treatment
facilities. Depending on the chemical, a certain percentage of
the load survives treatment and is then discharged to a
waterway. This study focused on homes associated with
treatment plants in Washington state (WA), USA, that
discharge to the lower Columbia River.
EXPERIMENTAL SECTION
A convenience sample of 20 households in Longview and
Vancouver, WA was recruited via newsletters, electronic mailing
lists, local businesses, and organizations. Researchers visited
homes to collect dust and laundry wastewater in 2011 and
2012. The homes sampled were all single family homes, 90% in
suburban and 10% in rural areas.
Dust was collected using a Eureka Mighty-Mite (model
3670G) vacuum tted with a cellulose lter (Whatman 2800-
199) held in the crevice tool with a stainless steel ring.
16
Researchers collected dust from primary living areas including
kitchen, living room, bedroom, oce, and dining room by
moving the crevice tool slowly across bare oor and carpet. A
sample of sodium sulfate was collected in the same manner
from a clean surface in place of a eld blank; no FRs were
detected (>1 ng g1) in this sample.
11
Participants prepared a full load of laundry to primarily
include clothing worn around the house, with type and number
of items tracked (i.e., pajamas, jeans; none appeared to be
specialty FR-treated work clothes). The home washing machine
was used to wash the clothing using Natural 2X Concentrated
Liquid Laundry Detergent (Seventh Generation, Burlington,
VT, USA) and warm water (detergent was separately analyzed
for FRs and none were detected). Samples (1 L) of the laundry
wastewater were collected in amber glass bottles at the end of
the agitation cycle, placed on dry ice in the eld, and stored at
<4 °C until analyzed. Blank water samples were collected prior
to addition of clothing and detergent.
A single grab sample (1 L) of inuent and euent was
collected in amber glass bottles from the Three Rivers Regional
Wastewater Treatment Plant in Longview, WA, and the Marine
Park Wastewater Treatment Plant in Vancouver, WA.
Collection of inuent and euent was timed so euent was
collected after the estimated residence time, collecting a plug
before and after treatment. Samples were stored on dry ice until
placement in a freezer (<4 °C).
Analysis of the Brominated FRs (BFRs). PBDEs (BDE-
28, -47, -66, -85, -99, -100, -153, -154, -183, -206, -209),
alternative-BFRs (alt-BFRs: BTBPE, DBDPE, TBB and
TBPH), and HBCD isomers (α-, β-, γ-HBCD) by ultra-
performance liquid chromatography (UPLC)-atmospheric
pressure photoionization (APPI) tandem mass spectrometry
(MS/MS) described by La Guardia et al.
32
was modied for
this study to include TBBPA and the ClOPFRs (TCEP, TCPP,
and TDCPP).
32
(Targeted analyte names, acronyms, and
chemical formulas are listed in Supporting Information, Table
S1, along with methodology and instrument setting.) Briey,
1 g (dry weight) sieved (300 μm) dust sample was subjected
to accelerated solvent extraction (ASE 200, Dionex, Sunnyvale,
CA, USA) with dichloromethane (DCM). Surrogate standards
(200 ng of 2,3,4,4',5,6-hexabromodiphenyl ether (BDE-166);
Cambridge Isotope Laboratories, Inc., Andover, MA, USA and
1000 ng of deuterated triphenyl phosphate (d15-TPP); Sigma-
Aldrich, St. Louis, MO, USA) were added to each sample prior
to extraction. Extracts were puried by size exclusion
chromatography (SEC, Envirosep-ABC, 350 mm ×21.1 mm.
column; Phenomenex, Torrance, CA, USA). Each post-SEC
extract was solvent exchanged to hexane, reduced in volume,
and added to the top of a solid phase extraction (SPE) glass
column containing 2 g of silica (Isolute, International Sorbent
Tech.; Hengoed Mid Glamorgan, U.K.). Each column was
eluted with 3.5 mL hexane (fraction one), followed by 6.5 mL
of 60:40 hexane/DCM, 8 mL DCM (fraction two), and 5 mL
50:50 acetone/DCM (fraction three). The second fraction,
containing PBDEs, alt-BFRs, and HBCD, and the third fraction,
containing ClOPFRs and TBBPA, were reduced and solvent
exchanged to methanol, and the internal standard decachlor-
odiphenyl ether (DCDE, 400 ng; Ultra Scientic, North
Kingston, RI, USA) was added to both fractions prior to
UPLC-APPI-MS/MS analysis.
FR Liquid Determination (Laundry Wastewater,
WWTP Inuent and Euent). Each sample (1 L) was
liquid/liquid extracted three times with DCM, 200 mL total.
Surrogate standards (200 ng BDE-166 and 1000 ng d15-TPP)
were added prior to extraction. The three extracts were
combined, solvent exchanged to hexane, and reduced in volume
(<1 mL). Post-extracts were puried by SPE, as noted for the
dust samples. Internal standard (DCDE, 400 ng) was added to
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each SPE fraction (two and three), and these were analyzed for
BFRs and ClOPFRs by UPLC- APPI-MS/MS.
Analytes in puried extracts were chromatographically
separated by UPLC (Acquity UPLC, Waters Corporation,
Milford, MA, USA) operated in gradient mode (100%
methanol (A1) and 100% water (B1)), equipped with a C18
UPLC analytical column (Acquity UPLC BEH C18, 1.7 μm,
2.1 mm ×150 mm, Waters Corp.). Analytes were ionized by
APPI; dopant (acetone) was introduced (150 μL/min) by a
liquid chromatography pump (LC-20AD, Shimadzu Corpo-
ration, Kyoto, Japan). Product and transition ions were
detected by triple quadrupole mass spectrometer (3200
QTrap, AB Sciex, Framingham, MA, USA) operated in the
multiple reaction monitoring (MRM) mode. Quantitation ions
for BFRs (mass to charge ratio, m/z) were m/z79 ([79Br])
and 81([81Br]), and m/z 35 ([35Cl]), 37([37Cl]) for
ClOPFRs and DCDE. Positive ions m/z342 and 343 were
monitored for d15-TPP quantitation. (Additional sample
preparation and UPLC-APPI-MS/MS operating conditions
can be found in Supporting Information).
Method validation was established by performance-based
QA/QC including method blanks, surrogate, duplicate, and
matrix spike analysis. (Surrogate recoveries are listed with the
sample results in Supplementary Tables S3, S5, S7, and S8).A
National Institute of Standards and Technology (NIST)
Standard Reference Material (SRM) #2585 (house dust) was
also analyzed; SRM #2585 mean % recoveries for PBDEs,
alt-BFRs, HBCDs, ClOPFRs, and TBBPA range 50
91%; individual recoveries range 38143%, Supplementary
Table S10). In laboratory blanks, FRs were not observed above
detection limits (>1 ng g1) in the rst batch (samples 01 to
09). However, trace amounts of TBB (4.2 ng g1), TBPH (7.7
ng g1), and TDCPP (16 ng g1) were detected in the blank of
the second batch. These amounts were subtracted from results
1020 for TBB and TBPH, as they were >10% of the lowest
detections (Quality assurance procedures including duplicate
and matrix spike results can be found in Supporting
Information, results in Supplementary Table S9).
RESULTS AND DISCUSSION
Household Dust and Laundry Wastewater. Levels of
FRs in household dust were obtained for 20 homes. A total of
21 FRs were detected; 16 were detected in 95% or more of the
homes. Laundry wastewater was also obtained from 19 of these
homes (one sample was lost during storage), and of the 21
compounds detected in dust, 18 were also detected in laundry
wastewater. Whereas the FR contribution to dust was
dominated by the three ClOPFRs, which contributed 72% of
the total (followed by PBDEs 19%, TBBPA 3.7%, alt-BFRs
2.9%, and HBCDs 2.5%), ClOPFRs were even more
dominant in laundry wastewater, at 92% of the total (followed
by BDE-47 at 2.5% and BDE-99 at 2.0%). This shift can be
attributed to these compoundshydrophilic nature together
with higher solubility and lower partitioning coecients
compared to other targeted FRs (see Supplementary Table
S1 for log Kow values). Each of the three ClOPFRs, two PBDE
congeners (BDE-47 and -209), TBB, and TBPH were detected
in 100% of laundry wastewater samples; other compounds
detected included seven additional PBDE congeners, BTBPE,
DBDPE, and HBCDs. TBBPA was not detected (>1 ng L1)in
laundry wastewater samples. Dust results are presented in
Figure 1, and composition of PBDEs and ClOPFRs in dust and
laundry wastewater is presented in Figure 2.
Laundry wastewater eld blanks were collected from 14 of
the 20 homes. Of the 22 analytes, TCEP (sample 8), TCPP
(samples 3, 8, and 18), and BDE-209 were detected in blanks,
but only BDE-209 was detected at levels >10% of the
corresponding laundry wastewater sample, in three blanks at
18%, 12%, and 21%. These values were subtracted from the
laundry wastewater analysis values for samples 8, 9, and 10. No
Figure 1. (ad) Household dust ame retardant median concentrations (ng g1, dry weight) and comparison results from previous studies. (Sample
collection dates).
Environmental Science & Technology Article
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analytes were detected in the surrogate eld blank. Individual
dust and corresponding laundry wastewater results by home
and analyte are listed in the Supporting Information,
Supplementary Tables S36.
Chlorinated Organophosphate Flame Retardants
(ClOPFRs). TCPP and TDCPP were detected in all dust
samples, and TCEP was detected in 95% of homes (ClOPFRs
dust results were obtained for 19 of the 20 homes due to
analytical issues). According to USEPAs 2012 Chemical Data
Reporting (CDR), 4,50022,700 tons/year of TDCPP were
manufactured or imported into the U.S. in 2010 and 2011;
TCPP was reported at 25,000 tons/year. According to the
CDR, TDCPP production has changed little since 1998; TCPP
volumes appear to have risen since 2006.
15,33
However, ICL
IndustrialProducts,amajorU.S.producerofTDCPP,
announced in 2012 that it would cease production of
TDCPP in 2015.
34
TCEP production fell between 2006 and
2012, but TCEP was also found at a level of 14% in the FR
Antiblaze V6 (2,2-bis(chloromethyl)propane-1,3-diyl tetrakis-
(2-chloroethyl)bis(phosphate) (Albemarle, Baton Rouge,
LA).
35
This product is primarily in automobile foam, with
production dating back to 1990 but levels not reported to CDR
for 2006 or 2012.
35
Of the 22 targeted FRs, TCPP was present in dust at the
highest level of any single chemical with a median level of 4,820
ng g1and a maximum of 82,700 ng g1. The primary use of
TCPP in homes is likely in polyurethane and polyisocyanate
insulation, and it has been found in the foam of some childrens
products such as car seats and changing pads.
3639
TDCPP, in
dust samples at a median level of 1,620 ng g1, has recently
been widely found in furniture foam as well as in childrens
products, although its use in childrens sleepwear was
withdrawn in 1977 due to its mutagenicity.
1,40,41
The median
dust level of TCEP (1,380 ng g1) was similar to that of
TDCPP. Median levels of TDCPP and TCEP were about half
of those reported in a 2011 California dust study by Dodson et
al., while TCPP levels were about twice as high as in the
California samples (Figure 1a).
2
Dodson et al. sampled the
same homes in 2006 (median levels 2,800, 5,100 and 2,100 ng
g1for TDCPP, TCEP and TCPP, respectively), suggesting a
decline for TDCPP and TCEP but a rise in TCPP exposure
(Figure 1a).
ClOPFRs were the FRs found at the highest levels in laundry
wastewater, and all three were detected in laundry wastewater
from every home. As with household dust, TCPP was found at
the highest levels, with a maximum of 561,000 ng L1and a
median value of 43,500 ng L1, followed by TDCPP with a
maximum of 65,600 ng L1and a median value of 13,500 ng
L1, and TCEP, with a maximum of 42,800 ng L1and median
value of 7,680 ng L1. The contribution of the individual
ClOPFRs to mean ClOPFRs was similar in dust and laundry
wastewater, with TCPP contributing 73% and 77%, respec-
tively, followed by TCEP (14% and 9%) and TDCPP (13% and
14%) (Figure 2). The similarity in proles in dust and laundry
wastewater may indicate that once released to the indoor
environment, these ClOPFRs have equal ability to collect on
clothing via dust and/or air. Clothing may then be acting as a
quasi-passive sampler, as previously suggested in several FR
studies of clothes dryer lint, transferring FRs, particularly those
that are more hydrophilic or water-soluble, to wastewater when
washed.
10,11,42
TCPP was also the most abundant ClOPFR
observed in several indoor passive air sampler studies.
43
Polybrominated Diphenyl Ethers (PBDEs). After the
ClOPFRs, PBDEs were the next highest in dust samples (n=
20): PBDEs ranged from 311 to 19,700 ng g1. BDE 209 was
the dominant congener in most samples. Total PBDE levels
were similar to those in 50 Boston homes sampled between
2002 and 2008 and those observed by Dodson et al. in 2011.
2,44
The median level of the penta-BDE formulation, which
includes congeners with 46 bromines, was about one-third
that of the 2006 samples tested by Dodson et al. (Figure 1b). A
larger study of 292 California dust samples collected between
2001 and 2007 and then again in 2010, however, reported little
change in concentration (Figure 1b).
45
The median level of BDE-209 (1140 ng g1), the major
PBDE in the deca formulation, was consistent with the 2006
and 2011 Dodson et al. report (1,400 and 1,200 ng g1,
respectively) and about half of levels reported in the larger
California study, 2,300 and 2,500 ng g1for 200107 and 2010,
respectively (Figure 1b).
2,45
Two PBDE congeners, BDE-47 and BDE-209, were detected
in laundry wastewater from every home, with median levels of
1,230 ng L1for BDE-47 and 140 ng L1for BDE-209.
PBDEs were detected in laundry wastewater at a median
level of 2,550 ng L1. Unlike the ClOPFR proles, the PBDE
dust and laundry wastewater proles were disproportional. The
dust prole favored the higher brominated, lipophilic PBDE
congener BDE-209, used primarily in television and electronics
casings, making up 50% of the mean PBDEs (Figure 2). The
laundry wastewater prole, however, favored the lower
brominated, less lipophilic congeners of the penta formulation,
particularly BDE-47 and -99, which contributed 46% and 36%
of the mean, respectively. The penta formulation was used
primarily in polyurethane foam, which can degrade and
produce low-density fragments.
46
These penta-BDE-containing
particulates may then become airborne, explaining the
dominance of penta-BDE congeners reported in passive
sampling of indoor air.
4749
This may also explain their
accumulation on clothing, whereas BDE-209 has been observed
to reside primarily in settled dust.
48,49
Tetrabromobisphenol A (TBBPA). TBBPA is used primarily
as a reactive FR (i.e., chemically bound to the polymer) in
Figure 2. ClOPFRs and PBDEs in dust and laundry wastewater,
percent composition (mean).
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printed circuit boards, with approximately 18% used as an
additive FR (no chemical bond) in acrylonitrile butadiene
styrene (ABS) resins and possibly in high impact polystyrene
(HIPS).
21,50
TBBPA was detected in 95% of dust samples (n=
19), with a median level of 209 ng g1. Levels were highly
variable, with the maximum detection (6560 ng g1) exceeding
those of BDE-47 (2600 ng g1) and -99 (5810 ng g1) and
several other FRs in the dust samples. Dodson et al. also
detected TBBPA in 100% of their 2011 and 94% of 2006 dust
samples.
2
Median levels were similar to our 2012 samples, at
200 ng g1in the 2011 samples and 260 ng g1in the 2006
samples (Figure 1c). TBBPA is considered the most heavily
used brominated FR, making up 59% of the total 2001 market,
with U.S. imports and production nearly tripling over the past
11 years (to 53,450 tons in 2012).
33,51
Despite its high usage
and 95% detection rate in the dust samples, TBBPA was not
detected in the laundry water samples. This may be explained
by the Abdallah et al. observation, with a modied passive air
sampler collecting both gaseous and particulate phases. They
detected TBBPA at levels approaching those of BDE-47, but
only in the particulate phase, whereas the lower brominated
BDEs as well as HBCD were detected in both particulate and
gaseous phases.
47
Batterman et al. also detected TBBPA in 90%
of oce dust samples, but only in 30% of oce air samples.
48
This may be related to TBBPAs lower vapor pressure,
compared to PBDEs and HBCD, as well as product usage:
since its primary use is reactive, the chemical bond may restrict
its mobility once incorporated into products.
Alternative Brominated Flame Retardants (TBB, TBPH,
DBDPE, and BTBPE). TBB and TBPH were detected in each of
the dust samples (n= 20), a detection rate nearly double that of
a 20022007 study of Boston homes.
1
Median levels of TBB
and TBPH, 190 and 115 ng g1, respectively, were similar to
those in the 2011 California samples taken by Dodson et al.,
but the maximum levels were much higher in the California
study (for TBB, 5900 compared to 1430 ng g1, and for TBPH,
3800 compared to 435 ng g1) (Figure 1c). TBB and TBPH are
components of Chemtura products Firemaster 550 and BZ-54,
used in polyurethane foam; another Chemtura product, DP-45,
is used in PVC plastic and other applications and contains
TBPH.
5254
TBB and TBPH were also detected in 100% of
laundry wastewater samples. Median concentrations were 363
ng L1for TBB and 445 ng L1for TBPH. The TBB-related
fraction (ftbb) of the total concentration of TBB plus TBPH
(ftbb = TBB/(TBB + TBPH) was lower in the laundry
wastewater (ftbb = 0.45) than in the dust samples ( ftbb = 0.69)
but similar to that observed in the air over the Great Lakes,
which ranged from 0.26 to 0.54, possibly indicating that TBB
and TBPH on clothing are associated with air levels.
52
A 2012 study of 102 couch foam samples collected from U.S.
households found these FRs in 13 samples, primarily from
couches purchased after the penta-BDE phaseout.
19
Three
studies tested foam from childrens products and found TBB
and TBPH in 17% of 101 items currently in use in 2011, in 5%
of 20 products newly purchased in 2011, and in 52% of
products newly purchased in 2013, indicating this combination
is becoming one of the primary replacements for penta-BDE in
childrens products.
36,37,55
DBDPE, structurally similar to BDE-209, has been marketed
as the replacement for the deca-BDE formulation used as an
additive FR in HIPS, ABS, and polypropylene plastics and in
textiles.
56
Its 2012 U.S. production volume was reported at
22,70045,400 tons.
33
DBDPE was detected in house dust
from all homes sampled (range 18490 ng g1, median 173 ng
g1), in the same range as for TBB and TBPH. Dodson et al.
also detected DBDPE in all samples, with median values nearly
tripling between 2006 and 2011 (from 51 to 140 ng g1)
(Figure 1c).
2
BTBPE, another PBDE replacement product (for
octa-BDE), was rst introduced in the 1970s and is now used in
ABS, HIPS, thermoplastics, thermoset resins, polycarbonate,
and coatings.
56
Its metabolism may yield the neurotoxic
compound tribromophenol.
57
BTBPE was detected in 80% of
the dust samples, with a range of <1 to 361 ng g1, somewhat
higher than levels observed by Dodson et al., which ranged
from 3 to 130 ng g1.
2
Although both DBDPE and BTBPE compounds were found
in household dust from 80% or more of homes and DBDPE
was detected in 74% of laundry wastewater samples, BTBPE
was detected in only 5% of the samples. Median levels of
DBDPE in dust were approximately twice those of BTBPE. A
Swedish dust and air study of ve households detected BTBPE
in each dust sample and DBDPE in four but detected DBDPE
in only one air sample.
49
Hexabromocyclododecane (HBCD). The three isomers of
HBCD (α-, β-, and γ-HBCD) were detected in 95% of dust
samples, at levels approximately 1 order of magnitude lower
than PBDEs or ClOPFRs, but higher than other FRs. HBCD
concentrations ranged from <1 to 3160 ng g1, with a median
concentration of 300 ng g1, nearly double the Dodson et al.
median values of 190 ng g1(2006) and 160 ng g1(2011)
(Figure 1d).
2
In the California study, the dominant
diastereomer detected was γ-HBCD, with median levels 49%
and 46% of median HBCD in 2006 and 2011, respectively; in
our samples, α-HBCD dominated (64% of HBCD) (Figure
1d). The technical product is dominated by the γ-isomer
(>90%), but enrichment to α-HBCD occurs following exposure
of HBCD-treated thermoplastics and textiles to elevated
temperatures (>160 °C), which can occur during product
manufacturing or through biotransformation.
5,58
The primary
uses of HBCD in the home are likely in expanded and extruded
polystyrene foam insulation (EPS and XPS) and to a lesser
extent on upholstery textiles.
20
A signcant shift from γ-toα-
HBCD in dust samples has been observed after exposure to
natural light.
59
Also, spatial variability can aect isomer proles,
with decreasing γ-HBCD and increasing α-HBCD concen-
trations with distance from HBCD-containing products.
60
Therefore, collection techniques and light exposure may have
contributed to prole variability between these studies.
HBCDs were detected in only 26% of laundry wastewater
samples, with HBCD levels ranging from <1 to 1,270 ng L1.
The stereoisomer prole of one laundry wastewater sample was
dominated by the γisomer, contributing 80% to HBCD in
that sample (Home 4, Supplementary Table S6). This was
considered an outlier, and when it was removed from the data
set, we observed similar isomer proles in dust and laundry
wastewater, with α-HBCD contributing 69% and 63% to mean
HBCD, respectively.
HBCD has been added to the Stockholm Convention on
persistent organic pollutants because of its persistence,
bioaccumulation, and toxicity, with phaseout under the
Stockholm Convention beginning in 2014.
61,62
The United
States is not a party to the Convention, but the USEPA
initiated an action plan on HBCD in 2010 and recently released
a draft Alternatives Assessment.
63
Wastewater Treatment Plants. To evaluate laundry
wastewater contributions of FRs to the aquatic environment,
Environmental Science & Technology Article
dx.doi.org/10.1021/es502227h |Environ. Sci. Technol. XXXX, XXX, XXXXXXE
inuent and euent were collected from two WWTPs, Marine
Park and Three Rivers, WA, and analyzed for FRs. These
WWTPs serve predominantly households (>80%), with some
industry discharges, none of which are known FRs dischargers,
and service the communities where the dust and laundry
wastewater samples were collected. Both utilize activated sludge
treatment and process approximately 10 million gallons per
day. Three PBDE congeners (3PBDE: BDE-47, -99, and
-209), TBB, TBPH, DBDPE, and three ClOPFRs (TCEP,
TCPP, and TDCPP) were detected in inuents. The ClOPFRs
were present at by far the highest levels, with mean inuent
levels of individual compounds ranging from 393 to 3,440 ng
L1;ClOPFRs were 6,140 ng L1at Marine Park and 1,680
ng L1at Three Rivers. 3PBDEs were detected in inuent at
206 ng L1at Marine Park and 35.0 ng L1at Three Rivers. In
euent, two PBDEs (2PBDE: BDE-47 and -209), TCEP,
TCPP, and TDCPP were detected. Euent 2PBDE levels
were 28.2 ng L1at Marine Park and below detection at Three
Rivers. Euent ClOPFRs were 11,800 ng L1at Marine Park
and 2,900 ng L1at Three Rivers (Supplementary Tables S7
and S8).
These levels of ClOPFRs are somewhat higher than those
found by the USGS at nine WWTPs discharging to the
Columbia River in 200809. TCEP in those euents ranged
from 160 to 650 ng L1, compared to our results of 814 and
563 ng L1at Marine Park and Three Rivers, respectively
(Supplementary Tables S7 and S8). TDCPP in USGS samples
ranged from 120 to 690 ng L1, compared to our results of
3,250 and 579 ng L1(Supplementary Tables S7 and S8). The
USGS study did not include TCPP, but it was measured in
WWTP euents and surface water of the Rhine Valley in
Germany.
30
Euent levels of ClOPFRs in that study typically
ranged from 5 to 400 ng L1, with TCPP at the highest
concentrations, and surface water samples varied from 13 to
310 ng L1, with TCPP again at the highest concentrations.
TCEP and TCPP were also detected along Californias San
Francisco Bay and the Southern California Bight, with mean
concentrations of 410 and 7.6 ng L1, respectively.
64
Indicating
resilience to treatment, these ClOPFRs were also detected in
the source water and nished drinking water of eight U.S. water
utilities, with median drinking water concentrations of TCEP
and TCPP at 120 and 210 ng L1, respectively.
65
PBDE concentrations were substantially lower in euent
than in inuent; previous studies indicate that PBDEs partition
primarily to sewage sludge.
26
No PBDEs were detected in the
euent from the Three Rivers plant, and the Marine Park plant
showed an 86% removal rate (Figure 3; Supplementary Table
S7). High removal rates (100%) were also observed for TBB,
TBPH, and DBDPE. By contrast, there was an increase in
TCEP, TDCPP, and TCPP levels at Three Rivers; at Marine
Park, TCPP increased, and TCEP and TDCPP decreased
slightly (Figure 3; Supplementary Tables S7 and S8). Although
treatment retention times were taken into account during
collection, similar observations have been reported and
presumed to result from uctuations in inuent concen-
trations.
6668
Alternative explanations could include analytical
interference from the complex inuent matrix.
To gain a general understanding of the importance of
laundry water in contributing FRs to WWTP inuent, estimates
were generated of expected levels of FRs if laundry wastewater
were the sole source. To create these estimates, we multiplied
the median level of the compound by 7.8% to account for the
proportion of inuent from laundry water and by 81%
(obtained from each WWTP) to account for the proportion
of inuent from residences.
6971
Interestingly, the estimates
generated are comparable to measured mean inuent
concentrations at the two WWTPs (Figure 3a,b; Supplemen-
tary Tables S7 and S8). Based on these observations, laundry
wastewater may well be a primary source of these FRs to
WWTP inuent and for ClOPFRs, with their ability to resist
treatment, to the aquatic environment.
Estimated mass loadings to the Columbia River were
calculated using average yearly discharge from the WWTPs
sampled. The highest estimated loadings were for TCPP, at 114
and 22.1 kg/year, and TDCPP, at 48 and 7.3 kg/year, followed
by TCEP, at 12 and 7.1 kg/year, from Marine Park and Three
Rivers, respectively. Considering that the U.S. generates more
than 85 trillion liters of wastewater annually, if the euent
levels detected at these plants represent WWTP loadings
nationally, approximately 402,000 kg of TCPP, or 2% of its
annual production, and 174,000 kg of TDCPP, or 14% of its
annual production, are being discharged annually to the aquatic
environment. This was also observed in a Swedish study,
reporting inuent loadings representing up to 5% of
compoundsreported use.
66
While PBDE levels in house dust were approximately one-
third of ClOPFR levels, PBDEs were present at comparatively
low levels in laundry wastewater and WWTP inuent and even
lower in euent. ClOPFRs, on the other hand, were found at
the highest concentrations in house dust and were also present
at relatively high levels in laundry wastewater as well as WWTP
inuent and euent. These data indicate that several factors
aect the transfer of FRs from products in the home to WWTP
euent and ultimately waterways. First, use patterns determine
the extent to which the compound is present in the household
dust and air. Second, our results suggest that hydrophilic
compounds accumulate at a higher rate in laundry wastewater.
Finally, a number of studies have demonstrated that
compounds that are highly soluble, resilient to microbial
Figure 3. (a,b) Flame retardants in wastewater treatment plant
inuent and euent and estimated ame retardant contribution of
laundry wastewater to inuent (*removal rate < 16%).
Environmental Science & Technology Article
dx.doi.org/10.1021/es502227h |Environ. Sci. Technol. XXXX, XXX, XXXXXXF
degradation, or with low partitioning coecients (e.g., log Kow
< 2) are ineciently removed during wastewater treatment and
thus discharged into aquatic environments.
26,72
The three ClOPFRs identied here, the compounds found at
by far the highest levels in the wastewater euent, combine all
of these factors, making them more likely to be present in
discharges to the environment. Some are high production
volume compounds, used in many products in the home in an
additive fashion, and have been shown to be resilient to
wastewater treatment.
While this study was somewhat limited in sample size, with
20 homes sampled, the variety of compounds analyzed
provided an opportunity to investigate factors aecting transfer
of a range of FRs with varying chemical properties including
solubility. These ndings should inform public policy on use of
FRs in products in the home by highlighting transfer of these
compounds to waterways such as the Columbia River.
ASSOCIATED CONTENT
*
SSupporting Information
Detailed instrument methodology, QC/QA, and individual FR
results. This material is available free of charge via the Internet
at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Phone: 206-632-1545 x119. Fax: 206-632-8661. E-mail:
eschreder@watoxics.org.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This paper is Contribution No. 3387 of the Virginia Institute of
Marine Science, College of William & Mary. The authors wish
to thank the study participants, the volunteers who assisted in
sample collection, and Dr. Hiro Tamura and Lorelei Walker for
their assistance in data analysis and gratefully acknowledge the
support of Columbia Riverkeeper.
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Environmental Science & Technology Article
dx.doi.org/10.1021/es502227h |Environ. Sci. Technol. XXXX, XXX, XXXXXXI
... The current study may have some limitations to acknowledge, despite the interesting findings that the downward trend of AHFRs relative to Harrad, 2017Harrad, , 2018Ali et al., 2011;Dodson et al., 2012;Drage et al., 2020;Harrad et al., 2008;Larsson et al., 2018;McGrath et al., 2018;Newton et al., 2015;Schreder and La Guardia, 2014;Tao et al., 2016;Tao et al., 2019) and this study. a BEH-TEBP was not determined in 2006a, 2006b and 2019. ...
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Since commercial polybrominated diphenyl ethers (PBDEs) have been globally banned or restricted in 2000s, alternative halogenated flame retardants (AHFRs) appear increasingly dominant over PBDEs in many countries/regions. In this study, low levels of AHFRs were unexpectedly observed in the indoor dust from Adelaide, South Australia. Anti-dechlorane plus (anti-DP) was the most frequently detected AHFR with median concentration of 1.28 ng/g, while other AFHRs were less detected (detection frequency < 50%). The levels of ΣPBDEs (496 ng/g, median) and ΣAHFRs (160 ng/g) and the ratio of ΣAHFRs/ΣPBDEs (0.32) were much lower than those investigated in Australian indoor dust previously. The findings were different to the trend for PBDEs and AHFRs from other countries over the past two decades. No significant correlation was determined between DP and PBDE congeners, indicating their different sources in dust. The human exposure assessment suggested that dust ingestion was the predominant pathway of PBDEs and AHFRs exposure for toddlers, while dermal absorption may be the dominant pathway for adults. The estimated daily intake (EDI) suggested low health risks via dust ingestion and dermal contact for general populations in Adelaide. This study contributes to the knowledge on region-specific FR contamination in indoor environments and related human exposure risk.
... On the other hand, the diastereoisomer profile can further confirm the possible source. In this study, γ-HBCD percentage at site S18 (82%) was consistent with the value of laundry wastewater (80%) (Schreder and La Guardia 2014). At the other sites, γ-HBCD percentage (27-42%) was close to the value of municipal wastewater (14-30%) (Ruan et al. 2019). ...
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The occurrence and health risk of hexabromocyclododecane (HBCD), a brominated flame retardant with its three diastereoisomers, in drinking water sources in the lower Yangtze River in China was investigated. Its concentration ranged from 0.58 to 3.71 ng/L and averaged at 1.18 ng/L. Among the three diastereoisomers of α-, β- and γ-HBCD, γ-HBCD was the dominant one accounting for 44% (ranging 27–82%) to the total concentration. Source of HBCD in the contaminated site was discussed according to its spatial distribution and diastereoisomer profile. The margin of exposure (MOE) approach was applied to evaluate the health risk of HBCD through drinking water by estimated exposure and derived reference dose. The MOE was 17 for adults and 12 for children in the worst-case scenario, suggesting a trivial health concern.
... Wastewater likely represents a significant pathway for OPEs to the Bay, and the Lower South Bay in particular. Due to their ubiquitous presence in a variety of consumer products, OPEs are frequently found in indoor dust and air (Stapleton et al., 2012;Wei et al., 2015;Rodgers et al., 2018), and can transfer from clothing and other textiles that, when washed, result in down-the-drain discharges of OPEs to sewers (Schreder and La Guardia, 2014;Saini et al., 2016). Of the 13 OPEs analyzed in 2013, 12 were detected in final effluent from at least one of three participating WWTPs discharging to the Bay (Σ 13 OPEs 3100-7900 ng/L; Sutton et al., 2019). ...
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Organophosphate esters (OPEs) and bisphenols are two classes of industrial chemicals that are ubiquitously detected in environmental matrices due to high global production and widespread use, particularly in the manufacture of plastic products. In 2017, water samples collected throughout the highly urbanized San Francisco Bay were analyzed for 22 OPEs and 16 bisphenols using liquid chromatography-electrospray ionization-Q Trap-mass spectrometry. Fifteen of the 22 OPEs were detected, with highest median concentrations in the order TCPP (42 ng/L) > TPhP (9.5 ng/L) > TBOEP (7.6 ng/L) > TnBP (7.5 ng/L) > TEP (6.7 ng/L) > TDCIPP (6.2 ng/L). In contrast, only two of 16 bisphenols, BPA and BPS, were quantified, with concentrations ranging from <0.7–35 ng/L and <1–120 ng/L, respectively. BPA and a few OPEs (EHDPP and TEHP) were primarily present in the particulate phase, while BPS and all other observed OPEs were predominantly found in the dissolved phase. Pairwise correlation analysis revealed several strong, positive correlations among OPEs, and few weak, negative correlations between OPEs and BPA, suggesting differences between the two classes with respect to their sources, pathways, and/or fate in the environment. Concentrations of OPEs and bisphenols observed in this study were generally consistent with reported concentrations in other estuarine and marine settings globally. TDCIPP exceeded existing predicted no-effect concentrations (PNECs) at some sites, and six other compounds (TCrP, IDDPP, EHDPP, TPhP, TBOEP, and BPA) were observed at levels approaching individual compound PNECs (not considering mixture effects), indicating potential risks to Bay biota. These results emphasize the need to control releases of these contaminants in order to protect the ecosystem. Periodic monitoring can be used to maintain vigilance in the face of potential regrettable substitutions.
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The rapid growth in the global production of organophosphate esters (OPEs) has resulted in their high environmental concentrations. The low removal rate of OPEs makes the effluents of wastewater treatment plants be one of the major sources of OPEs. Due to relatively high solubility and mobility, OPEs can be carried to the coastal environment through river discharge and atmospheric deposition. Therefore, the coastal environment can be an important OPE sink. Previous studies have shown that OPEs were widely detected in coastal atmospheres, water, sediments, and even aquatic organisms. OPEs can undergo various environmental processes in the coastal environment, including adsorption/desorption, air–water exchange, and degradation. In addition, bioaccumulation of OPEs was observed in coastal biota but current concentrations would not cause significant ecological risks. More efforts are required to understand the environmental behaviors of OPEs and address resultant environmental and health risks, especially in the complicated environment.
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Rapid urbanization and industrialization in the eastern seaboard region of China enhance the widespread use of organophosphorus flame retardants (OPFRs). The present study set up a coupled WRF-CMAQ-SMOKE and multi-compartment exchange modeling framework to assess the environmental fate and cycling of OPFRs and their contamination in the Bohai and Yellow Seas' marine food web. The framework predicts meteorological conditions, optimized air emissions, and concentrations of OPFRs in air, seawaters, marine sediment, and the food web. The model was implemented to simulate the temporal and spatial fluctuations of Tris (2-chloroisopropyl) phosphate (TCPP), the most dominant congener of OPFRs in China, in the Bohai and the Yellow Sea ecosystems on a spatial resolution of 10 km. Results revealed the effects of source proximity, atmospheric transport and deposition, and the changes in meteorology on TCPP's temporal-spatial distribution across different areas of coastal waters. The model also captures TCPP levels in commercial fish species in the Bohai Sea. The detailed temporal-spatial characteristics of TCPP with the mesoscale resolution provide useful information and a new tool for the environmental and health consequences of mariculture, urban and industrial emission mitigation in coastal regions for emerging chemicals, and fishery industry development.
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Tris(1,3-Dichloro-2-propyl)phosphate (TDCPP) is an organophosphorus flame retardant (OPFR) widely used in a variety of consumer products (plastics, furniture, paints, foams, and electronics). Scientific evidence has affirmed the toxicological effects of TDCPP in in vitro and in vivo test models; however, its genotoxicity and carcinogenic effects in human cells are still obscure. Herein, we present genotoxic and carcinogenic properties of TDCPP in human liver cells (HepG2). 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and neutral red uptake (NRU) assays demonstrated survival reduction in HepG2 cells after 3 days of exposure at higher concentrations (100–400 μM) of TDCPP. Comet assay and flow cytometric cell cycle experiments showed DNA damage and apoptosis in HepG2 cells after 3 days of TDCPP exposure. TDCPP treatment incremented the intracellular reactive oxygen species (ROS), nitric oxide (NO), Ca2+ influx, and esterase level in exposed cells. HepG2 mitochondrial membrane potential (ΔΨm) significantly declined and cytoplasmic localization of P53, caspase 3, and caspase 9 increased after TDCPP exposure. qPCR array quantification of the human cancer pathway revealed the upregulation of 11 genes and downregulation of two genes in TDCPP-exposed HepG2 cells. Overall, this is the first study to explicitly validate the fact that TDCPP bears the genotoxic, hepatotoxic, and carcinogenic potential, which may jeopardize human health.
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BFRs (brominated flame retardants) are a class of compounds that are added to or applied to polymeric materials to avoid or reduce the spread of fire. Tetrabromobisphenol A (TBBPA) is one of the known BFR used many in industries today. Due to its wide application as an additive flame retardant in commodities, TBBPA has become a common indoor contaminant. Despite the detection of TBBPA and its derivatives in various environmental and biological samples, information on its occurrence in biota is scarce. TBBPA has been shown to possess immunotoxic, cytotoxic, thyroid hormone agonist, estrogenic activity, reproductive, hepatotoxicity, teratogenicity and neurotoxicity in previous studies. In this review, we evaluated the environmental occurrence of TBBPA (and its derivatives) in different environmental compartments using various analytical techniques, the transformation of TBBPA into various derivatives and the toxicity of TBBPA and its derivatives as well as outlining the possible mechanisms of actions. This review will go a long way in closing up the knowledge gap on the silent and over ignored deadly effects of TBBPA and its derivatives and their attendant consequences.
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Tris(1,3-dichloro-2-propyl) phosphate (TDCPP) has received concerns due to its frequent detection in environmental media and biological samples. Our previous study has indicated TDCPP reduced the lifespan of Caenorhabditis elegans (C. elegans) by triggering an unconventional insulin/insulin-like growth factor signaling (IIS) pathway. This study continued to investigate the possible deleterious effects of TDCPP relating to longevity regulation signal pathways and biological processes. Specifically, this study uniquely performed small RNA transcriptome sequencing (RNA-seq), focusing on the underlying mechanisms of TDCPP-reduced the longevity of C. elegans in-depth in microRNAs (miRNAs). Based on Small RNA-seq results and transcript levels of mRNA involved in the unconventional IIS pathway, a small interaction network of miRNAs-mRNAs following TDCPP exposure in C. elegans was preliminarily established. Among them, up-regulated miR-48 and miR-84 (let-7 family members) silence the mRNA of daf-16 (the crucial member of the FoxO family and pivotal regulator in longevity) via post-transcription and translation dampening abilities, further inhibit its downstream target metallothionein-1 (mtl-1), and ultimately contributed to the reduction of nematode longevity and locomotion behaviors. Meanwhile, the high binding affinities of TDCPP with miRNAs cel-miR-48-5p and cel-miR-84-5p strongly support their participation in the regulation of nematode mobility and longevity. These findings provide a comprehensive analysis of TDCPP-reduced longevity from the perspective of miRNAs.
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We assessed constructed wetland (CW) performance in the removal of six emerging pollutants (EPs) from university campus wastewater. The EPs considered were: diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n-octyl phthalate (DNOP), bis(2-ehtylxexyl) phthalate (DEHP), tris(1-chloro-2-propyl) phosphate (TCPP) and caffeine (CAF). Six pilot-scale CWs, i.e., three horizontal subsurface flow (HSF) and three vertical flow (VF), with different design configurations were used: two types of plants and one unplanted for both the HSF and the VF, two hydraulic retention times (HRT) for the HSF, and two wastewater feeding strategies for the VF units. The results showed that the median removals in the three HSF-CWs ranged between 84.3 and 99.9%, 79.0 and 95.7%, 91.4 and 99.7%, 72.2 and 81.0%, 99.1 and 99.6%, and 99.3 and 99.6% for DEP, DIBP, DNOP, DEHP, TCPP, and CAF, respectively. In the three VF-CWs, the median removal efficiencies range was 98.6–99.4%, 63.6–98.0%, 96.6–97.8%, 73.6–94.5%, 99.3–99.5% and 94.4–96.3% for DEP, DIBP, DNOP, DEHP, TCPP and CAF, respectively. The study indicates that biodegradation and adsorption onto substrate were the most prevalent removal routes of the target EPs in CWs.
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Indoor environments have elevated concentrations of numerous semivolatile organic compounds (SVOCs). Textiles provide a large surface area for accumulating SVOCs, which can be transported to outdoors through washing. A multimedia model was developed to estimate advective transport rates (fluxes) of 14 SVOCs from indoors to outdoors by textile washing, ventilation, and dust removal/disposal. Most predicted concentrations were within 1 order of magnitude of measurements from a study of 26 Canadian homes. Median fluxes to outdoors [μg·(year·home)-1] spanned approximately 4 orders of magnitude across compounds, according to the variability in estimated aggregate emissions to indoor air. These fluxes ranged from 2 (2,4,4'-tribromodiphenyl ether, BDE-28) to 30 200 (diethyl phthalate, DEP) for textile washing, 12 (BDE-28) to 123 200 (DEP) for ventilation, and 0.1 (BDE-28) to 4200 (bis(2-ethylhexyl) phthalate, DEHP) for dust removal. Relative contributions of these pathways to the total flux to outdoors strongly depended on physical-chemical properties. Textile washing contributed 20% tris-(2-chloroisopropyl)phosphate (TCPP) to 62% tris(2-butoxyethyl)phosphate (TBOEP) on average. These results suggest that residential textile washing can be an important transport pathway to outdoors for SVOCs emitted to indoor air, with implications for human and ecological exposure. Interventions should try to balance the complex tradeoff of textile washing by minimizing exposures for both human occupants and aquatic ecosystems.
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US building codes balance the consideration of hazards to public safety, health and general welfare. Current codes require foam plastic insulation materials to have both protection by a thermal barrier and compliance with Steiner Tunnel test requirements. The Steiner Tunnel test is met by adding flame-retardant chemicals to the foam. Studies demonstrate that the Steiner Tunnel test does not give reliable fire safety results for foam plastic insulations. Foams that meet the Steiner Tunnel test still pose a fire hazard if used without a code-mandated thermal barrier. Insulations protected by a thermal barrier are fire safe and the use of flame retardants does not provide any additional benefit. Evidence is examined of the health and ecological impacts from the added flame-retardant chemicals. Changing the building codes could prevent health and environmental harm from the toxicity of these substances without a reduction in fire safety. Plastic foam insulations that are protected by a thermal barrier should be exempted from the Steiner Tunnel test and the need to use flame retardants. This change would align US codes with code regulations in Sweden and Norway and ensure the fire safety as well as improve health and environmental impacts. Les codes de construction américains prennent en compte de manière équilibrée les dangers pour la sécurité publique, la santé et le bien-être général. Les codes actuels exigent que les matériaux d'isolation en mousse de plastique possèdent à la fois une protection assurée par une barrière thermique et une conformité aux exigences des tests en tunnel Steiner. Il est satisfait à l'essai en tunnel Steiner par l'ajout à la mousse de produits chimiques retardateurs de flamme. Les études démontrent que l'essai en tunnel Steiner ne donne pas de résultats fiables en matière de sécurité incendie concernant les isolations en mousse de plastique. Les mousses qui satisfont à cet essai présentent encore un risque incendie en cas d'utilisation sans une barrière thermique prescrite par un code. Les isolations protégées par une barrière thermique sont ignifuges et l'utilisation de retardateurs de flamme n'apporte aucun avantage supplémentaire. Sont examinés les éléments probants relatifs aux incidences sur la santé et l'environnement des produits chimiques retardateurs de flamme qui sont ajoutés. La modification des codes de construction pourrait prévenir les dommages en matière de santé et d'environnement dus à la toxicité de ces substances sans réduction de la sécurité incendie. Les isolations en mousse de plastique qui sont protégées par une barrière thermique devraient être dispensées de l'essai en tunnel Steiner et de la nécessité d'utiliser des retardateurs de flamme. Ce changement alignerait les codes américains sur les règles des codes en vigueur en Suède et en Norvège et garantirait la sécurité incendie tout en améliorant les incidences sur la santé et l'environnement. Mots clés: codes de construction sécurité incendie retardateurs de flamme inflammabilité isolation santé publique Tunnel Steiner barrière thermique toxicité
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Although recent usage of organophosphate (OP) flame retardants has increased substantially, very few studies have reported on OPs in biota including wildlife, and essentially there is no information on OP body compartment composition and in ovo or in utero transfer for any given wildlife species. Concentrations and patterns of sixteen OP triesters were presently screened for and/or determined in six body compartments from female herring gulls (Larus argentatus; n = 8) and the separate egg yolk and albumen of their entire clutches of eggs (n = 16) (collected in 2010 from a Lake Huron colony site, Laurentian Great Lakes of North America). Fat (32.3 ± 9.8 ng/g wet weight; ww) contained the highest OP concentration, followed by egg yolk (14.8 ± 2.4 ng/g ww) ≈ egg albumen (14.8 ± 5.9 ng/g ww) > muscle (10.9 ± 5.1 ng/g ww) > red blood cells (1.00 ± 0.62 ng/g ww), whereas in liver, blood plasma, and brain all OPs were not detectable. Nine OPs accumulated in herring gulls, but the concentrations and proportions of OPs were dependent on the body and egg compartment. For example, tris(2-butoxyethyl) phosphate (TBOEP) accounted for 66 % of the ΣOP concentration in albumen, but only for 13 % in yolk. Tri-n-butyl phosphate (TNBP) accounted for 25 % of the ΣOP concentration in yolk, but was not detected in albumen. Estimates showed that overall OP burdens in the body (3.5 μg) were greater than in the whole egg (1.2 μg), although depuration via in ovo transfer was substantial.
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Long-lived and high trophic level marine mammals are vulnerable to accumulating often very high concen- trations of persistent chemicals, including pesticides, industrial by-products, and flame retardants. In the case of killer whales (Orcinus orca), some of the older individuals currently frequenting the coastal waters of British Columbia (BC) were born during the First World War, well before the advent of widespread chemical manufacture and use. BC's killer whales are now among the most polychlorinated biphenyl (PCB) contaminated marine mammals in the world. While the "legacy" PCBs have largely been banned, polybrominated diphenyl ethers (PBDEs) have recently emerged as a major concern. The endocrine-disrupting nature of these two persistent fire retardants in biota spells trouble at the top of the food chain, with increasing evidence of effects on reproductive health, the immune system, and development in exposed mammals. The heavy contamination of BC's killer whales, coupled with their long life span and high trophic level, highlights the need for a "weight of evidence" approach in research, conservation planning, and regulatory deci- sions. Given the global nature of contaminant dispersion, such approaches can only be effective when carried out on both national and international scales.
Article
Few studies have measured the flame retardants polybrominated diphenyl ethers (PBDEs) in the indoor environment. Here, we report measurements of PBDEs in house dust samples collected from the Washington, D.C. metropolitan area in the United States. Dust samples were analyzed for 22 individual PBDE congeners and our results found PBDEs present in every sample. Concentrations of total PBDEs ranged from 780 ng/g dry mass to 30 100 ng/g dry mass. The dominant congeners observed in the dust samples were congeners associated with the pentaBDE and decaBDE commercial mixtures. Ancillary data were collected on the homes and examined for any correlations with total PBDE concentrations. No correlations were observed with year of house construction, type of flooring (i.e., hardwood vs carpet) or the number of television sets or personal computers in the home. However, a significant inverse correlation (p < 0.05) was observed between the area of the home and the contribution of BDE 209 to the total PBDE concentration in dust. Using estimates of inadvertent dust ingestion (0.02-0.2 g/day) by young children (ages 1-4), we estimate ingestion of total PBDEs to range from 120 to 6000 ng/day. Clothes dryer lint was also sampled and analyzed for PBDEs from five of the homes and were present in all five samples ranging from 480 to 3080 ng/g dry mass. This study demonstrates that PBDEs are prevalent at relatively high concentrations within homes where people, and particularly young children, may be susceptible to exposure.
Article
Levels of 12 organophosphate flame retardants (OPs) were measured in particle phase samples collected at five sites in the North American Great Lakes basin from March 2012 to December 2012 (inclusive). The target compounds were three chlorinated OPs [tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP)], three alkyl phosphates [tri-n-butyl phosphate (TnBP), tris(butoxyethyl) phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP)], and six aryl phosphates [triphenyl phosphate (TPP), tri-o-tolyl phosphate (TOTP), tri-p-tolyl phosphate (TPTP), tris(3,5-dimethylphenyl) phosphate (TDMPP), tris(2-isopropylphenyl) phosphate (TIPPP), and tris(4-butylphenyl) phosphate (TBPP)]. Total OP (ΣOP) atmospheric concentrations ranged from 120 ± 18 to 2100 ± 400 pg/m3 at the five sites, with the higher ΣOP levels detected at Cleveland and Chicago. ΣOP concentrations at these urban sites were dominated by the chlorinated OPs (TCEP, TCPP, and TDCPP), with the sum of these three compounds comprising 51 ± 6 and 65 ± 12% of ΣOP concentrations at these two sites, respectively. Nonhalogenated OP compounds were major contributors to ΣOP concentrations at the remote sites, with the sum of all nine nonhalogenated OP concentrations comprising 70 ± 21 and 85 ± 13% of the ΣOP concentrations at Eagle Harbor and Sleeping Bear Dunes, respectively. On average, these ΣOP concentrations are about 2–3 orders of magnitude higher than the concentrations of brominated flame retardants in similar samples.
Article
Brominated flame-retardant (BFR) additives are present in many polymeric consumer products at percent levels. High environmental concentrations have been observed near cities and polymer, textile and electronics manufacturing centers. Most studies have focused on European, North American and Asian locales. Releases are likely rising most dramatically in countries with weak environmental and human health regulation and enforcement, demand for electrical and electronic equipment (EEE) is escalating, and importation of waste EEE occurs. Several African countries meet these criteria, but little data are available on burdens or sources. To better understand the extent of BFR environmental dissemination in a southern African urban community, inland and coastal sediments were collected in the eThekwini metropolitan municipality, South Africa, and analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), 2-ethylhexyl 2,3,4,5-tretabromophalate (TBPH), 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE). BFRs were detected in all samples (n=45). Concentration data are presented on total organic carbon (TOC) normalized basis. ΣBFR ranged from 114 to 47,100 ng g-1. Decabromodiphenyl ether was detected in 93% of samples (mean concentration 3208 ng g-1) followed by TBB at 91% (mean conc. 545 ng g-1). Durban Bay is strongly influenced by urban runoff and tidal hydrology and sediments therein exhibited ΣPBDE concentrations ranging from 1850 to 25,400 ng g-1 (median conc. 3240 ng g-1). These levels rival those in the heavily impacted Pearl River Delta, China. BFRs likely enter the South African environment during manufacture of BFR-containing products, during and following product use (i.e. after disposal and as a result of materials recycling activities), and from nonpoint sources such as atmospheric fallout and urban runoff. These results underline the need to investigate further the environmental burdens and risks associated with BFRs in developing countries.
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Increased use of flame-retardants in office furniture may increase exposure to PBDEs in the office environment. However, partitioning of PBDEs within the office environment is not well understood. Our objectives were to examine relationships between concurrent measures of PBDEs in office air, floor dust, and surface wipes.We collected air, dust, and surface wipe samples from 31 offices in Boston, MA. Correlation and linear regression were used to evaluate associations between variables. Geometric mean (GM) concentrations of individual BDE congeners in air and congener specific octanol–air partition coefficients (Koa) were used to predict GM concentrations in dust and surface wipes and compared to the measured concentrations.GM concentrations of PentaBDEs in office air, dust, and surface wipes were 472 pg/m3, 2411 ng/g, and 77 pg/cm2, respectively. BDE209 was detected in 100% of dust samples (GM = 4202 ng/g), 93% of surface wipes (GM = 125 pg/cm2), and 39% of air samples. PentaBDEs in dust and air were moderately correlated with each other (r = 0.60, p = 0.0003), as well as with PentaBDEs in surface wipes (r = 0.51, p = 0.003 for both dust and air). BDE209 in dust was correlated with BDE209 in surface wipes (r = 0.69, p = 0.007). Building (three categories) and PentaBDEs in dust were independent predictors of PentaBDEs in both air and surface wipes, together explaining 50% (p = 0.0009) and 48% (p = 0.001) of the variation respectively. Predicted and measured concentrations of individual BDE congeners were highly correlated in dust (r = 0.98, p