PII: So@45-6535(97)10133-3 Charles A_ Staples

Chemosphere, Vol. 36, No. 10, pp. 2149-2173, 1998
Q 1998 Eisevier Science Ltd
All rights r&xnd
priacd in Great Britain
0045-6535198 $19.00+0.00
Pergamon
PII: So@45-6535(97)10133-3
ABEWEW OFTEE ENVIBONMENTAL FATE, EFFECTS, AND EXPOSUBES OF BISFHJllNOLA
Charles A_ Staples’, Philip B. Dom2, Gary M. Klecka3, Sandra T. O’Blook’,
and Lynne R Harris*’
Assessment Technologies, Inc., Fairf& VA 22030, USA’
Shell Development Company, Houston, TX 77082, USA2
The Dow ChemicalCompany,Midland,MI 48674, USA3
A&tech Chemical Corporation, Pittsburgh, PA 152 19, USA’
Society of the Plastics Industry, Washington, DC 20006, USA’
(Received
in Germany 6 August
1997; accepted 14 @%i~r 1997)
ABSTBACT
B&phenol A (CAS 85-05-7) may be released into the environment through its use and hand&g, and
pen&ted discbrrges. BPA is moderately sohble (120 to 300 mg/L at pH 7), may adsorb to sediment (Koc 3 14
to 1524), has low volatility, and is not persistent based on its rapid biodegradation in acclimated wastewater
treatment plants and receiving waters(half&es 2.5 to 4 days). BPA is “slightly to moderately” toxic (algal EC,
of 1000 pg/L) and has low potential for bioaccumulation in aquatic organisms (BCFs 5 to 68). The chronic
NOEC for Daphnia mugnu is >3 146 pg/L. Surfjlce water concentrations are at least one to several orders of
magnitude lower than chronic effects, with most levels nondetected.
01998 Elsevier Science Ltd. All rights reserved
JNTBODUCI’ION
Bisphed
A
Bisphenol A is a commo&~ used name fix 2,2-(4,4-d
propane (Figure 1). The structure
of BPA is obtained &om the combination of 2 moles of phenol with one mole of acetone, as desc&ed below.
2149
2150
Bisphend A Marmrfacruring
BPA is m
by two dif&mt methods. The firat condenses phenol with acetone under low pH
md~~~inthep~~ofcatafysts~oltrlystpronloters.BPAisthenp~
uaiq d&&&ion technology. Molten puSed
di&mmt malyats and puriktkm
product is &red
and dried. The second is similar, but uaes
technology that generate fkwer wastes. The dried BPA (Produced by either
~)formsprills,fhlresor~W~areg~~inthe~~procese(wndliapreeidueaad
was&water). BPA may also be inadvertently released as fugitive dust emissions fknu closed systems during
promsa& ham-U@, and transportation. In 1993, an estimated 109 tons or 0.017% of the 640,000 metric tons
BPAproducedwererepoltedas~toair,~wrter,orwast~~trsrmrantp~ts,withans~
0.085% recycled, landfiued or incblerated.
Bisphenol A Use
Most (99.9%) domestic@
produced BPA is uaed by the mam&tmmssauiutemediateintbe
production of polycarbonate and epoxy resins, flame reta&&,
and other qmialty products. Final products
in&de adhesives, protective coatings, powder paints, automotive lenses, protective window gbz&,
buildkg
materials, compact disks, optical lenses, themal paper, paper coatiugs, as a developer iu dyes, and for
encapsulation of elect&l
and electronic parts. Wastes created during the uae of BPA to mamktme
~andproduas~~chaing~Imlordia&hertn&aswenas~~orother
releases.
H3C
Figurel.Molecular-of
CH3
A @PA).
other
2151
Review
ofBPA Fate, Eflpectr amiEpa_wre
~~thepateasirlreleasestotheenvimnmmt,theIlkinwtl?~emd~ofBPAwereexrmined.
obje&ves oftbis study were to mview, a) available data on the physical chara&&tics
that control the di&bution
and tie
of BPA in the emvirm,
The
and remval me&a&ms
b) toxioological data fbr BPA to aquatic
orgpnismgc)~endpredicted~~wotercanceatrations,an4d)toaeseaothe~s~
predicted exposure concentration data and predicted no e&cts umcentratims.
Under ambient con-
BPA is a solid and is sold as q&als,
elevated temperatures during mauuthctu@
prills or flakes. While BPA is molten at
(melting point=150-155 “C), releases to the emimmmt
are
gmmlly dissolvexlia water or are in the form of particulates (Table 1). BPA has a reported water soh%lity of
120-300 mg/L [2,28]. The U.S. Envir-
Protectim Agency (EPA) [20] cites an unliskd reference that
states that BPA has greater solubility at alkaline pH values due to its disassociation umstants, pKa 9.6 to 10.2
f321.
Ochnol- Water Partition Cck@cients
Measured and estimated octanol-water partition coefficient vahw (log Kow or log P) fk BPA are
shown in Table 2. The log Kow was measured to be 2.20 Wang reverse-phase HPLC [15]. Koremm
aud
Gorokhov [3 l] conducted a study of the extractability of BPA from water using a series of oqymic solvents at
pH=3, where the s&bibty is lower than expected at typical ambient pH values of 6-8, and mmsumd a log Kow
of 3.32. Bayer reported a log Kow value of 3.40 [2]. Blancbard [4] caldatd
ammptkm
a v&e of 3.82 using various
fimu Lyman [34]. ‘l%ev&e of 3.40 mamred by Bayer [2] was mwurcd
at mbiaa pH values and
so is believed to be the best log Kow value for BPA
Soil-Sediment Sorption Constant
Meaaned~sOrption~Koc~havenot~reportedHowud[28]crlcuktedKocvrloes
of 3 14 to 1524, using a water sohbility of 120 mg& and a log Kow of 3.32 (Table 2). These sorption data
indicate that soil and sediment are mode& sinks EDrBPA mleascd to the gromd or to surfke water.
2152
Table 1. Physical and Chemical Propertim of
Value
Puometer
lkfeqme
CAS No.
W-05-7
Molecular Weight
228 g/mol
Formula
C,J-&&
specilic Gravit$
1.060 s/cm’
[541
1.195 gh2
WI
22OC(at4mmHg)
WI
398 C (at 760 mm Hg)
El41
HO-155 c
I281
157 c
1141
9.59, 10.2
1321
11.30
I561
120,000 pglL
VI
300,000 pgL
I21
4.OE-8 mm Hg
I281
3.96E-7 mm I-Q
P41
8.7OErlO mmHjj
I21
3.96B9 mm Hg
[21
Boiling Point
Melting Point
PG
Water Sobbil@@
Vapor Pressure*
* Values measured at 20 to 25 “C.
Vapor Pressure and Henry's Conrtmt
The vapor pressure for BPA reported by Howard [28] is 4.OE-8 mm Hg (Table 1). The rathoIs [28]
calculated a ms
umstant (H) of l.OE- 10 atm-m3/mol (Table 2) &om this vapor pressure, aqueous sol&i&y
of 120 mgk., and molecular weight. Chemicals with H values < 1.OE-7 atmm3/mol are con&red
low-vobtility,
as the chemical is leas volatile than water [28]. Tberefore, BPA is a low volat%ty compound in the em&mm&.
Bioconc&ration
fktors
for BPA were measured by MlTI [41] that ranged &om 5.1 to 13.8
(dimensionless uuits) for a 42&y test conducted at 150 pg/L and <20 to 68 for a test conduc&
at 15 &L
2153
(Table 2). Kawamhi [30] reported a value of <lOO. Wimated BCFs were cahxlated from water soh&ility or log
Kow by Howard [28] using techniques pmsented in Lyman [34]. These techniques, however, do not account for
m&bolic~
Bstimsted BCFs of 42 to 1% were calculated [28]. The U.S. EPA would &mi@ BPA as
“not a bionccum&&e
chemical of concern” [21] because the measured and predicted BCFs are substantially
less than 1000, the concern threshold fix bioaccumulationibiomagni6cation.
As suggested by Gillette [24],
compounds such as BPA with measured BCFs less than 100, are classitied as having low potential for
bioaccurmlatioa. Given the cfisassociationconstants of 9.6 and pH of 8, as found in some &&v&r
case in saltwater, the expected bioconcentration
or as is the
potential of BPA would be less than predicted with
undisassociated BPA uuder acidic pH conditions.
Table 2. Partitioning Cbara&risties
Value
Parameter
Log Kow
Log Koc for soil
and sediment
Bioconcentration
Factor (BCF)
Henrys Constant
for Bispbenol A.
Comment
Reference
2.20 (dimensionless)
reverse-phase HPLC
WI
3.32
shake flask, pH 3
]311
3.40
measured
PI
3.82
calculated Tom Lyman [34]
141
‘314 (dimensionless)
calculated from sohMity
WI
1524
calculated from log Kow
WI
5.1-13.8 (dimensionless)
measured, 42 da, 150 pg/L
]411
<20-68
measured, 42 da, 15 pg/L
1411
42
calculated from solubility
WI
196
calculated from log Kow=3.32
Lw
l.OE-10 atmm3/mol
calculated from vapor pressure
PI
and sohbilitv
FATE OF BPA IN TEE Eh’VIRONMENT
Several biotic and abiotic Sue processes act to disperse and degrade BPA upon release into the
emmommab. Besides mixing within the water cohmm, BPA is subject to biodegradation adsorption to nrspended
solids and se&men& and possibly photodegmdation. BPA is not expected to appreciably vohttihze or hydrolyze
in natural waters. BPA vapor is subject to atmospheric photooxidation. The following discussion presents
available infixmation on pertinent abiotic and biotic degradation mechauknrs.
2154
ofBPA us&a
Atleast17testshavebeenperhmodmeasuringthebiotraatrbilityaud
closed bottles, some type of inoculum, and that measured the loss of parrmt BPA, oxygen consuqth,
production of COP Achievement of 100% reduction ia ThOD is essuhlly
equhht
of oxidizsble par& compound. CoIktively, the data attest to the rqid biodegradatk
and wastewater -t
or
to 100%
ofBPA iu s&k
w&m
plants using both unacclimated and acclimated mkobial po~uktions.
‘Ihe ready biodegradability of BPA was measured by Mobil Oil Corporation [42] using non-acclimated
sewage and soil seed with a U.S. EPA procedure equivaht
to OECD Method 301B, the mod&d Stmm test
that~CO,~~Thesewageseedwasobtained~omamunioiprlsewrrgetr~pLntmdthe
soil obtaiued i?om within a forest near the experhe&al facility. BPA was “readily” biodegradable as 83.6% of
ThCO, was produced in 28 days [42]. Recently, Goodwin and West [25] reported that BPA was readily
biodegradable using OECD Method 301F, the manometric respirometry test, acbieviug 81.0 to 93.1%
biodegradation in 28 days They also reported extekve
minerahtion,
with 76.3 to 90.6% of ThCOz produced
in28dayaA20dayshldybytheDowChemicalCompany[13]repoaedaBOD,of71%ofThODHlithBPA
and umcluded that BPA was “madi&”-le..
In contrast, two studies by Stone and Watkinson [52] also
usingthe Closed Bottle and Sturm tests with non-acclimated sewage seeds measured ins&i&nt
degradah
to
conclude that BPA was “readily” biodegradable [50]. The Closed Bottle Tests are the most stringent “ready”
biodegradability tests iu use due to their low concentration of inoculum.
BPAiseasilydegmdediubiologicalwastewaste
‘Ihe “i&rent” bh@ad&@
sys@nsandinstudkthatsimulatewastetre&ment.
of BPA was exam&d by Tumer and Watkiuson [53] in a 30 day mod&d semi-
continuous
activated sludge (SCAS)
assay. The SCAS test, which is a “draw and @l” eqeh&al
design,
measured the aerobic degradation of BPA and &ported au 87-95% aerobic degradation of BPA withk 30 days
[53]. BPA was called “inherently” biodegradable. Matsui [37,38] found BPA to be “easily decomposed” iu
acclimated treatment facilities in Japan. Studies of industrhl wasteweter treatme& fici&ies iu Japau receivhg
BPA-containing wastewater, measured 72% COD removal and 57% BOD removal iu 24 br [37]. Primary
biodegradah
in an activated sludge treatment system with acclimated populations removed >99% of the BPA
consumption
biodegradation
primary
wastewster treatment
efficiency
-Biolopical
biodegradation
wastewater
River DieAway
co* production
Modified Storm Test
Primary
BPA oxidation and
BOD,
and CO2 production
02
co* production
MUSlWed
Endpoint.(a)
Closed Bottle Test and
Demand (BOD)
Bioohemical Oxygen
(OECD method 301F)
Mauometric respirometry
Modified Sturm Test)
OECD method 30 1B
U.S. EPA test (similar to
Study Type
ReSUlta
and Chemical Treatment
of Biaphenol A.
loss of BPA in 3 to 5 days with acclimated
days;
>99.8% BPA
ppq outfall: <0.05-0.08 ppm BPA, overall reduction of
decant pond at plant: 46.9 ppm BPA distribution box: 8.8
microbial populations, BPA was “readily” biodegradable
overall, 36%
Houston Ship charmel seed: t,=4.0
receivhg stream seed: t,,=2.5 da
efhlent seed: t,,=3.0 da
“ready” biodegradability criteria in these two tests
degradation in mod&d &u-m Test; BPA did not meet
no oxidation of BPA in Closed Bottle Test, insufkient
BPA was “readily” biodegradable
BOD, = 71% of ThOD
BPA was “readily” biodegradable
production in 28 days, 10 day time limit met;
81.1 to 93.1% Oz ummmption and 76.3 to 90.6% TWO,
BPA was “readily” biodegradable
83.6% of ThCO* produced ia 28 days;
Table 3. Biologically Mediated Degradation
[481
1111
1521
P31
1251
[421
Reference
SCAS Assay
reduction of BPA in
wastewater
method study
BPA
removal and recovery of
wastewater
reduction of BPA in
_ fiio&
aerobic biodegradation
Wastewater treatment
fkom wastes
Recovery &kiency of BPA
mehod study
Wastewater treatment
30-d modikd
containiug wastewater
Biotreatmtmt of BPA-
primary biodegradation
primary biodegradation
Extended aeration, activated
shxlge system
removal of BPA
EndDoinffs) Measured
BOD and COD
Studv TvDe
of Bisphenol A (cant).
Results
and Chemical Treatment
and eflhent measured, >92%->96% removal of BPA
&ration of prwitates,
XAD resin absorption of
.succes@Uy removed BPA in waste
chemical/physical pretreatnxmt followed by anaerobic biotreatment
BPA fkom clari6ed water; >85% removal of BPA possible
pH neutrahtion,
short-chain aliphatic acids were left
electrochemical oxidation with high NaCl and iaitial pm 10; only simple
87-95% aerobic degradation in 30 days, BPA “inherently biodegradable”
>99% removal achieved, >87.5% COD removal in 14-da
activated shulge treatment with populations acclimated after 14-da,
inhent
decomposed” by acclimated treatment kilities
72% COD removal in 24 br, 57% BOD removal in 24 hr; BPA “easily
Table 3. Biologically Mediated Degradation
1471
[lOI
PI
[531
[231
WI
137,381
Reference
2157
and >87.5% of the COD in two weeks [23]. Jn a study of the e&iency of the fMity [email protected]
sy&aq Shell Dcveeopment Company [48] reported >99.8% reduction iu BPA levels between a decaut pond and
its o&Ml (M
not detect&
at the limit of analy&l
detection). The Dow Chemical Company [ 121 reported
that >92% to XX% of the BPA waa removed between the i&uent and eMuat
of a was&water treatment
-V-m
BPAisnotexpactedtobe~inaafuoe~Rivadieaway~~performedtomeasure
primary biodegr;ldrtion of BPA [ 111. Dom [ 1 l] used water colhxted from a BPA mauu&turiq
e&z&,
the &ili@+s mceiviq
ficil$+s
stream, and the downstream Houston Ship Channel into which the re&ving
stream &wed. The water samples and a deionized water control were placed iu glass contaiaerq spiked with
BPAtoaconoentcationof3OOO&L,audhehiat22to25DCfor8daysNolossofBPAintheumtroloccurred
BPA mans
began declining witbiu 48-hr iu all non-control test systems. Concentrptions were
no&&c&d
(cl00 &L) by day 3 with the *s
rec&in g stream water and were nondetected by day 5 iu
the other two systems, indicating 96% to 97% loss of BPA within 3 to 5 days. Half-lives were cakadated to be
3.0 days, 2.5 days, and 4.0 days for the tests using e&ent,
r eceiviog stream and downstream channel,
respectively. Based on these results, it can be conchded that BPA is rapidly biodegraded in the environment.
Miu&ialpop&kms
appear to rapidly acclimate to degrade BPA [ll-13,23,38,42].
tests that were carried out for 30 days by Funm [23], showed exteaudve deg&ation
Biodegradation
of BPA as the microbial
popuhtions became acclimated Peter day 14. At study end, 39% removal of BPA was achieved. Wastewater
treatment
systems that routinely treat BPA-co&a&g
biodegradation.
wastewater achieve costly
high levels of
With acclimated microbial populations, >87% to >99% removal of BPA is achieved in
wa&wa@rtrsrtmrmtsy&msandiathe
em&mment. The ease with which microbial populations adapt to BPA
is cansiatent with the rapid biodegradation of BPA observed under the conditions it has been tested.
Researchers have studied the biodegradation pathway of BPA and identified the key degradation
metabolizes [33,49]. Using a speci6c strain of gram-negative bacteria called m-1
isolated f&n a treatment
plant rec&ing BPA-wrstewrt er, L.obos [33] and Spivak [49] identified major and minor pathways of biological
degradation.
hydrom
The major pathway produced two primary metabolites, 4-hydroxyaceteph~one
and 4-
acid. These compounds rapidly degmded to CO2 and water or were incorporated into bacterial
cells ‘Ihe m&r pathway also pmduced two primsry metabolitq 2,2-bis(4-hydroxyphenyl)- I-propauol followed
by conveasion to 2,3-bis(4-hydroxyPhenyl)-l,2-propaoediol. Additionally, Lobes [33] calculated that 60% of the
carbon went to CO, 20% went to bacterial cell growth and 20% went to miscellaneous sohrble organic
compounds.
2158
Abiotic Wamuwter Treatment
An~~~mdrhcoPlcPt~Eatrerringwr~ewster~BPAhave~~~
(Table 3). Gemical and phy&cd prcbertmrpl t (incWng
pH control) of BPA-containing wassowatex wese
combined, followed by anaerobic biotreatment [471. &ma [47J reported that success&d BPA reduction was
addeved &hougb penx&qes were. not reported. In another f&i&y, Crook [lo] described a BPA removal and
recovery q&em that wag used to treat a uunplex waste atream. The waste &eam contained 280-6700 ppm
p~mckdmgBPATrtrbneatincludedpHneu$lJizltion,filmtianofprecipitates,anduseofwieusxAD
resing for adsoqtkm of BPA fIom cbnitied water. Greater than 85% recovery of BPA was poszible l?om this
overall process. More recently, Boecolo [6] reported that BPA was reduced ia a higb NaCl and bigb pH
~aSmg~~BPAwre~~remnoved~donlyIlimple~~-chm~c
acids were le& In general, bioW&wnt
of BPA-contain&
wastewater appears to be the treatment method of
choice; however, various abiotic treatment proossees appear to e@bctively aid the removal of BPA &om
wastewater.
!smilaroxid8nts.BothprocesM
cenoccurinwateraudintbentmqhere.
Aocordiqg to Howard [28], EPA
abWpt.ion ofuvligbt
exceed&29Oilm
(sunlight)innsosnlandaoidio-~o~~Howad[28]also~~BPAinbasicmoskaaol
solution exhibited @&ant
absorption of UV >290 nm. This indicates
wateqaswenrstbeatmosphere.speciticexte&ofphotolysiEinWteris
turbidity, watertlnI&We,
and others) and the amom& of
may photo@ze in surf&e
on w&r conditions (pq
reaoaiagtbewateraur&e.Atmo6pbelic
photodsgpsdrtionoft89QII%rmmurrtofvaporpBu#BFA~yooaurby~~~duetoin~with
hydroxy radicals or photoly&. Pa&al&e
BPA mry be removed by depo&ion and p&ly
deaivrtive of BPA [28]. Howmd [28]-S&W
of66hrto
16Odaysmtdthat&boxne8pAmsybeve
photo&&s.
thatpboW&&tkmofBPAiuwateswouMhsvekalf-lives
h&&es
ofo.74-7.4 hr.
2159
Pm&tedE
Llistrihtim
Dis@utionofBPAiuthe
approach [36]. Fug*
of BPA
-twasest&tedu??&theMackayI&vel1&gacitymodolitlg
can be ngarded as tho “escaping tandency” of a chemical substance &II a phase.
~b18~ofplaaeun(eg.PII)mdiarclatedtooonccmtrrtion~afU%rcitycrpacityoonamt,Z,with
Unas of mole&&s.
distriis
Ev&ative -
models such as Mackay Level 1 allow tho e&n&m
of relative
of chemicals l&asfxl into tbo envinwment without seeking to predict actual -al
concentrations. Actual -
umce&ations
can only be predicted with co&lcnce
011spatially and
temporaSly J.&ted scale systems. The Mackay Level 1 modeling approach was used hero to e&mate relative
.
.
~I&WOSM of BPA witbin di&ent m
unmpatmnts. This a&roach utilizes key physical properties
to m
how a chemical may become distributed among those compartments. Tbis approach does not consider
possible degradation, only the compound’s tendency to dishiie
among environm&al
compattments.
Tho MackayLevel 1 modeling approach calculates envkonmental distr&utions within a hypothetically
sized ‘ti-w&I”.
‘Ike uoit-world has compartments of 1111
atmosphere, soil, surf& water, sediment, sospended
solids (any solid matter ia suspension within tho water c&mu) and aquatic biota. Rolative vohrmes of each
compntqwnt mtd de&y characte&tics wcfc dewed
for soil, sedime@ mspended solids, and biota based
on model de%& v&es (Table 4). Fhy&sl property data used were aqueous soh&iiity, vapor pres&nre, soil and
se&me& d&r&u&m coe&ient
(Kd) and bioco~~~~tration factor (BCF). Fugacity capacities were calcolated
fbr ea& comparbne&. Relative numbefs of moles compartment were oak&ted
moles in each compartment. &gradation
as was the perceatrge of total
was ignored for these oakxdations.
Table 4. Mackay Level I Environmental Bistribution of Biaphenol A.
Computmont
Volme
(m’)
Media Ben&y @g/m’)
M(moles)
Pereeatagc (%)
Air
6E+9
1.19
0.0002
<<l
soil
4. SE+4
2400
24.63
25
Water
7E+6
1000
52.36
52
Biota
7
1000
0.0036
<l
Suspended
35
1500
0.0239
<l
2.1E+4
2400
22.98
23
Total-100 moles
Total=lOO%
solids
Sediment
2160
These-addmsedthegeneraldimib&mofBPAr
ktotheeavkommt.mreadts
~~thrtsbout5oo/oofthe~BPAwDuldtrpidtobindto~orsoilswith
iuthe water udumn. Traces of BPA would be associated with swpemded solids and biota. N
w~be~withtheatmospheae.Theee~areredlectiveofBpA’sv~~voporp~e,~s
constant, and modest aqueous soh&ility. Any tmdegraded BPA in sortice water esmklly
win go to the
seclimartaEven~~ofBPAmryp~intobiaqqtheamtustissmYnsbrcebi~~islow,
and organims (e.g., fish) may metabolically reduce any BPA to which the orgaoimn is intern&
di&&&ms cakulated here demon&rate the tendency of BPA that enters the ekmmmt
eqmed.
The
to dkkbute ammg
compartments. Chemicals entering the air, water, soil, s&ment and suspended solids would degmde. Actual
eminmmntal
charaot~~s
contribute to determing
linal conmktrations.
AQUATIC TOXIClTY
ThetoxicityofBPAtoaquatic
orgaGmshaEbeenstudiadwklgsewxalqeciesaudtrophiGlevelsiaboth
fresh and salt water (Table 5). The toxioity of BPA to mkobial
p
was detei&ed
&z&water Pseudomoms spcks. A study by Febig [22] u&g PseW
>320,OOO&L.,baaedonthe~ofa
IO%decreamincellgrowth.
puti& rqwti
StoneaudW
u&g two
a~ l&hEC,
of
[521rap&
al
IC,, of 54,500 @L, based on inhibition of growth, u&g Psetuhmorw jhwwcens.
Algae
~er[l]repoaedtheresuhsofa~of6hOLttezmteaspeorwaPed~ordingtoGoodLabontoTy
Prackes (GLP) in MMnmnt of an EPA Test Rule [ 193, using i?esb and salt water algae, iuvertebrates and fish.
Aithough short-term in duration, algal tests conducted for >72 hours are considered l& cycle tests [55]. EC,,
v&es are applied to acute endpoints, while No Observed Eilkt Conce&atks
(NOEC) are related to chronic
testaBothacuteandchronicendpoimsweaecelculated~tbe~greeerlgaSe~~c~~~twn
(Table 5). A 96-h EC, based on cell counts was 2700 &L., while a 96-h EC, based on cell volume was 3100
&.
cm,
Ihe 9&h duxmic NOEC for this study was 1170 &.
For studies with the saltwater algae SkeIeronenta
the 96-h EC, based on cell unmts was 1000 &L and the 96-h EC, based on chlorophyll a content
was 1800 @.
A NOEC was not detenked.
Stephe4tson [5 l] reported a 96-h EC, of 2500 &,
cell growth, using Selanartrum cqtwicomutum.
based on
2161
Table 5. Aquatic Toxicity Studies for Bisphenol A.
Results
Organism
F/M
Test Type
Reference
Endpoint
Cl&L)
Pseuiomomvjluore.wens
F
18-k FJC,,
10% lass gmP&l
>320,000
WI
F
lC,O
growth inhibition
54,500
WI
cell count
2700
Ul
Selmraptrumcapricornutum
F
%kEC,
Selrmartrum
capricornutum
F
96-k EC,
cell volume
3100
PI
Selrmarirmn cqricorimtum
F
96-k Gkonic
cdl volume and cdl
1170
PI
NOEC
count
Selmrartrum capricornuh4m
F
96-k EC,,
=flgrowth
2500
r511
Skdetonema cost&m
M
96-k EC,,
call mlmt
1000
Ill
skeL?to?lma
cartahlm
M
96-k EC,,
ohlomphyu I!
1800
[ll
Water flea Daphnia magna
F
48-k EC,,
immobilimth
10,000
Ill
Watu flea Llaphnia magna
F
48-k EC,
imm~tion
3900
[511
WIta tlca Llaphnia mqna
F
48-k EC,
immobiliption
20,000
1271
Wetu flea Daphnia magna
F
21-d ckvnic
mollnlily and
23146
[31
flow-~
lqwoduction
mat&y
1100
PI
-tee
NOEC
M
96-k LC,,
Fatheadminnow Pimephale3 promeh
F
96-k LC,, et&
mortality
4700
PI
Fathead minnow Pinwphales promeh
F
96-k LC,, flow
molt&y
4600
VI
Rainbow bout Oncorhynchw myth
F
48-k LC,-LC,,
mortality
500&7000
1351
Rainbow tmut Oncorhynchus qvkiw
F
96-k LC,,
mo&iQJ
3000-3500
PI
Rainbow trout Oncorhynchu
F
96-k LC,,
mentality
Lake Emerald Shiner
F
72-k LC,,
Msdaks Oqzia~ lohpes
F
Mysid ekimp M)ddojnic bahta
u&
Atlsntic shide
Sheqhd
mykiw
Menidia menkiia
minnow Cyprinodon
4ooo
r451
m&&y
4ooo-6ooo
PI
48-k L’&
motility
15,ooo
[411
M
%k
mortality
9400
VI
M
96-k LC,,
mmtality
7500
[161
LC,,
variegafus
Note: F/M refers to fieshwster or marine species.
2162
Invertebrates
[I] who reported
neto~ofthe~wateriav~~~wasexrmiaedbyAlexrader
a 48-h EC,, of 10,000 &L (Table 5) [l]. In a shuiy using the saltwater myaid &imp, &jwi&@s
bahia,
Alewnder[l]~a48hEC,ofllOO~.A~by~[5l]marcnueda~~4&h
EC, of 3900 &L, baaed on B
Hend.&s [271 reported a 48-h EC, for Lhqhia magna of 20,000
,&L. Based on these data, BPA is classi4ied as Wgbtly to moderately toxic” to invates
[17]. Bayer [3]
performed a chronic bioassay using Lkphnia magna that measured the effacss of BPA on mortal& and
reproduction over 21 days under GLP comlitions. No e&&s to the daphuids were observed at any BPA test
concentratkm for either mortality or reproduction. The NOECs for both endpoints with Daphnia magna were
>3146 j&L [3].
Fish
Freshwater - Alexander [1] reported the results uaittg the &&ater
fithead mionow Pimphales
prunekzs (Table 5). The authors rqxnted a 96-h LC, of 4700 @L under static coaclitiona, and a 96-h IX,
4600 &
of
tinder &~-through umdi&ms. The ratio of the calculated &head minnow 96h:48-h LC,, data was
<l and accord& to the U.S. EPA, “s
of 3ooO-3500 &
was not iudkted
[ 191. Maud
Phil [46] repoxted a 96-h LC,,
using rainbow trout (&co+n.cchcls mykiss). Using the same specie4 Lysak and Mar*
[35] reported a 48-h LC, of 5000 &L and a 48-h LC,, of 7000 Ccgn. The 48-h LC, would be between 5000.
7000 &L. Another study by Reiff [45] measured a rainbow trout 96-h LC,, value of 4000 &L. A 72-h LC,
usiugLakeEmeraldshiaer&hwasreportedtobe4000-6000
&L
provided. Researchers from the Chemical Inspection and Testiag ktitute
[l]. No o&x details of the test were
ia Japan [41] measured a 48-h LC,
of 15,000 &L, using medaka oryzias latipes.
iubine - Alexander [l] measured a 96-h LCs, of 9400 @L u&g the saltwater iiah Atlantk silverside,
Menidia menidia (Table 5). A 96-h LC,, of 7500 ,ug/L was reported by JZmittoe [ 161 u&g the saltwater MI
sheepahead minnow, Cyprinadan variegatus.
2163
?? Algae-thsh
rAlgae-marine
OInvext-marine *Fish-fresh
rlvliaobes
): AlgaeNOEC
*Invert-h5h
0 Fish - marine
* Invert-NOEC
Figure 2. Toxicity of Bispbenol A to Aquatic Organkms
myaid &imp ibfjs*is
across ‘lkophic Levels.
buhiu were aligbdy more atmitive tbau the tiwlmmter alga Selenustrumc.qwicorn.utum
or the da&id Dqdmh magna. In contrast, the fkeabwater fathead mhmow Pimephales promeh
and rainbow
vykiss were dightly more semitive than the saltwater sbeepsbead mirmow Cyprimxkwz
trout Oncm~h
wikgatus. Oved,
slwrwam and acute test re&ts mnged f?orn 1000 to >320,000 J.&L and chronic test results
ranged f?om 1170 to >3 146 &L for a variety of species, tropbic levels, endpoints and test conditions.
BPA shows an absence of ckmkity (acute and chronic e&ct levels are similar) when aoute and chronic
data are compared The acute toxicity (48-h EC& of Duphiu magna ranged from 3900 to 20,000 &L, while
its chronic NOEC was >3 146 /#L based on mmta&y and reptoductioa Simkly,
of the green alga Selenaptrwn capric~tum
was 1170 &
tbe acute toxicity (96-h EC,)
ranged from 2500 to 3 100 @L., while the cluonic 9&h NOEC
based on cell counts and cell growth These data represent acute-to-chronic ratios (ACRs) of 1
to6,withanbutoneACRrrmging~lto3.Thekdrofchronicity~~whythemarinealgPS~~~~
cartdwn acute 9&h ECs, of 1000 &
is the lowest acute or chronic value available, in addition to potential&
beiog slightly more senaike than the &e&water algae &at was tested.
2164
EXPOSURE ANALYSIS OF BPA
Sources of BPA Entry into the Emironment
There are several potential routes of BPA entry into the enviromnent. At mamrfacturiug and processing
Ml&es, low levels of BPA are dimctly released to surface waters and the atmosphere via permitted dimharges.
Varioustypesofmgitive emisskms to air may occur while processing and haudling BPA during its manufkctnre
or use. Add&ma&
BPA theoretically could be released from various products that contain small amounts of
uureacted BPA or that are converted to BPA under specific conditions. This study focuses on the direct and
indirect discharges entering the enviromnent, rather than releases Born other sources.
SARA Title III Toxic Release Inventory (TM) Reporting of BPA
In the U.S., facilities manufacturing or handling specified amounts of certain materials must annually
report eslimamd releases of those chemicals to the enviromnent under the CommunityRight-to-Know
provisions
of the SARA Title III, Section 313, Form R reporting requirements. Releases, discharges, recycling and
tmatmmm ofthese chemicals are reported. Data from 1993 (the most recent year for which data were available
at the time of this study) were reviewed for the reporting man~cmrers
and processors of BPA Data consisted
of meamred or &xlated releases to air, snrBce water or publicly owued treatment works or sewage treatment
plants (KHWs). AJso reported were amounts ofmaterials sent o&ite for treatment, recycling, sale, or disposal.
In 1993, 107 BPA mauulhcturing and processing facilities reported releases to the environment [20].
Fromtbe five nuumfhcturing Glities,
a total of 482,000 kg of BPA (-9.075% of the approximate 640 million
kg produced) were recycled, landfiUed or incinerated, or were reported as releases to air, surface water, the
grouud, or PQTWs. Approximately 365 kg were reported as discharges from mam&cturing Mhties directly
to surface water, while no BPA was discharged to PQTWs. From the 102 BPA processing Sudiities, a total of
162,000 kg of BPA (-0.025% of the total BPA produced) were recycled, landWed or incinerated, or were
reported as releases to air, snr&x water, the ground, or PQTWs. Approximately 3400 kg were reported as
dimharges from 13 processing &ilities directly to surface water, while 14,900 kg corn 14 processing Mlities
were discharged to PQTWs. The remaining 80 Exilities do not discharge to surface waters or IWTWs.
Release data for 1993 were used to calculate potential surface water concentrations using general EPA
assumptions [20]. BPA released directly to snrface water was mixed into the low (7QlO) flows that were
obtained liomthe EPA’s ReachScan database (Table 6). A 7QlO low flow is the average flow over a single 7&y
2165
T&it 6. Em&matedSurhceWater
Rakviag
Relea8e
Concon@
at Low .Blow (TQ2Q)uf BPA
W8ten1 or POTWs (Ibed
Receiving
FIlCiliQ
O#H
streamLow
on 1993 TIU Reports).
Flow
rn4tream
V=)
concentration
rt Low
mow w)
1
1
2.88E+6
0.000011
2
1
2.89E+6
0.000011
3
3
79,300
0.0012
4
2
26,850
0.0024
5*
40
202,545
0.0063
6
1463
2.86E+6
0.016
7*
314
260,430
0.038
8*
12
6712
0.057
9
24
926
0.820
10
132
323
13
11
0.5
79,300
0.00002
17
17
219,900
0.00024
18
2.3
2060
0.0035
13
49
29,280
0.0053
16
12
2940
0.013
12
380
8638
0.14
15
3500
1481
7.5
19
6063
2152
8.9
14
3475
776
14
* Denotes mauticturing fbdit.ies
periodthatoccursonly once every 10 years.In&antaneous
umcentrah
were calculatedmsumkg thatno
&egndrtionor~loasesoccurred.RelcasestoPOTWsweretreatedshailatSexceptthrtBPAwasaacnuned
dqqadedby 90% ia thePOTW priorto discharge,
basedcmdatapreseatedin Table3. Basedon the mkkMity
of flowdata,concentratimwerec&&ted fix 1) thethreemmufrcturing
h&ties reporting365 kg of BPA
2166
reLmsestosur&ewater,2)~raweuofthe
waters(47%ofthetotalrepo@dby
1627 hg BPAmJoases to mrir&e
lOpmoe&@
processorsxat43)fMnineofth614pro@akg
hailitissrepomagabout
13,500 kg BPA mleaaes to PQTWs (91% of the total reported).
While this mmlysis does not account fix processes that remove BPA from the environn~&
to &t&e
it is useful
the @antaneous BPA concentration upon mixing in rec&ing waters. Using EPA’s procedure, the
e&m&d BPArecekg
stream con-
based on the low 7410 flow, ranged from a low of l.lE-5 &
toahjgbof14~withmostv~~~O.l~.~~~w&tnwcrenotavPilrblefortheremrining
eight k&ties
and are not shown Additionally, these calcu&tions ofiu-stream +xntcentmtions did not in&de
consideration of biodegradation, sorption to sedkn&
or other chemkal loss phenomena. Actual moeking
stream umcemmtions are expected to be much less &an these estimated concentrations.
Environmental Mombring Data forBPA
Few studies of BPA concentrations in the emmmment are available. The umal m&uique for an&z&
BPA h czmim&d
samples has been gas chromatographyknass spectroscopy (GCMS) [7,8,27,401.
High
Performance-Liquid Chromatography (HPLC) has also been used, espeoirfty with toxicity test samples and
atmospheric samples [5, 43, 501. More recent& Clarh utibred a technique called particle beam-liquid
chromatography (PB-LCIMS) while iuvestigathtg PCYlW ef&tant and Sniahed dtkhing water [7-91. This
te&dque was able to detect low levels of BPA in eftluent samples that were not detected by CC/MS. Ma&ham
[44] developed a technique using cool on-cohunn iajection / gas chromatorgaphy / electron impa
ioni&on
/
mass spectrometry to analyze BPA in surf&e waters that may receive BPA discharges.
In the early to mid-197Os, Matsumoto [39,40] ana&ed river water at various lo&ions in Japan (Table
7). The authors d&xtedBPA in only one sample, between 0.01-0.09 &L [39]. Bemlts for another 19 smfhce
water samples were mainly not detected (14 samples) with 4 samples ranging gem 0.06-0.11 &L and one
sanpleat1.9~[40].WarkbyHendriks[27]~theRhneRiverinwestaolEurope~~nodeQectddeBPA
(detection limit -0.01 &)
in 7 samples with one sample having 0.119 &L BPA To achieve low detection
limits, Hmdriks [271 conceaSratedtherntalytesof~Lwster~~ueiPgaXAD~SmfUcewrter~~s
conecteddownstmam 0fU.S. BPApmducemiu
1996 [44] were ahnond&ected (cl.0 a).
BPA was a&red
inthreepoTw~ts~botbpB-LcIMSaad~~oc/kfs~7,8].BPAwrs~~is~e
KYIWsamplethatrec&edno
at25,&Land8&L,respectively,
kput. Usblg PB-LCYMS, BPAwaa
butwasnotdemoteduaing
iUtlWdKZ&VO
s
GCYHS. &PA was not de&oted
in a single sample of Snished drinkug water using either PB-LCMS or CC/MS [9].
2167
6ooliters8Iuplas,xAD-resin
VI
cimeentr8t~;pulyzedwltb
GCIMS
v8fiou8
induserial
mid-
14 samples an co.01 /.4gn;
smnpleswllected 8t v8rious
md pristine waters,
1970s
0.06-O. 11 @IL (n=4)
thea between 19741978;
1.9 /.Jg/L (n=l)
alI@WJdWithGChfS
co.01 /@L (Hz);
2rhm3iuilldwtrialueas;
3rd sample was between
smple plqmtion
0.01-0.09 crgn
not spccifi6d,Gc/Msused
not detected (ND) by any
500 liter sample conect~,
an@tkal method
malyzed with PB-L4YMS and
Tokyo, Japan
Tama River, Japan
Fiaisheddrinking
1973
1990
water
WI
1391
techniques
[91
GCNS.
vwioustbluae
w8tersin
U.S.
1996
15 upstreamand 15
WI
downs&em samplea (8t edge
of mixing zme) fin all U.S.
Aquatic Eflect~ Asawnent
qfBPA Emdronmental C-trattm
-lhnmwumlmdestirmtted-expo~-ofBPAweaeoompueddireotlywith
available toxicity data. Detected and e&mated surfice water cmm&&ms
nonWed.
Measured mrfiwe water con-s
were all low, with most values
(hpmese rivers and Rhine River studies from the 1970s
and1989,relpadivdy)~wge~bdowddactimlanits(in23of3Osrmp~~~stadies)withtha
single
recently~~~finrtheRhineRivarinEuropeof0.119~.Low~in-atraunBPAoanoattrrtions
~~U.S.relersedatawerel.lE-5to14~,withmostvrhresmnchlessthmO.l~.r)rtrue
show in Figme 3 as diarhtions
of the e&mated exposure commtratims. Nondetected values were assumed
to be equal to the detection limits.
2168
Figure 4. Comparison of BPA Chronic NOEC Valuea with Exposure Concentrstio~~
Acute and hronic data are available Enr freshwater algae and invertebra@? but not for marine species.
The available toxicity data showed ?ittle indication of chmicity”,
calculate potential chronic toxicity vahw from acute v&es
cozwrhvely
so an application &or
of 10 was used to
[19]. Chronic toxicity v&q
there&e,
are
expectedto be up to 10-f&l lower than acute toxicity values. The range of chronic NOEC vaiues
shown was determined by com&akg the lowest acute values for fisb, invertebrates, and algae that ranged fkom
1000 to 3250,ugL. Expected chronic values were c&a&ted to be betweeo 100 to 325 &
BPA. These v&es
are considerably lower than the available measured chronic v&es of 1170 to >3 146 @L BPA.
llte
comparison
of eshated
chronic valoes with all measore-d and predicted exposure unw&aku
shown in Figure 3. Measured and predicted BPA exposure wn~tion
is
data are premtted as disbhhw
reprewkd by the geometric mean, the 25% and 75% qwtiks, and the 5% and 95%tile values. The comparison
shows that there is approximately one- to eight-orders of magohde
exposure data and the estimated chronic values.
difkwx
between the di&b&ms
of
2169
SUMMARY
BPA is not expected to be persistent in the environment since it has been shown to pass a “ready’
biodegradation test, is easily degraded in acclimated wastewater treatment plants and recking
waters, and
photooxidizes as vapor phase BPA or deposits as particulates kom the atmosphere. In surf& waters, a study
using water from the receiving stream of a BPA manufacturer showed that BPA was rapidly biodegraded with
a reported >%% loss in 3 to 5 days and measured h&lives
of 2.5 to 4.0 days. Studies using municipal
wastewatertmatme& plant seeds, showed BPA to be “readily” biodegradable by measuring up to 90.6% ThCOz
produckm and up to 93.1% Oz m
in 28 days, while meeting the required 10 day time window. Actual
exposure monitoring data for BPA in environmental compartments are few. However, based on the available
measured and calculated surface water data, concentrations of BPA in suribce waters are expected to be low.
Similarly, modest amounts of BPA are expected to become sorbed to sediment, and also be removed due to
biodegradation. In the atmosphere, vapor phase BPA (a low percentage of airborne BPA) has an estimated
perskoce
of as low as a few hours, while par&late BPA would settle out of the atmosphere relatively rapidly.
Test results have shown that BPA has low potential to bioaccumulate in tkh. Bioconcentration factors
of 5 to 68 have been measured in fish and are lower than calcuhrted from octanol-water partition coefficients.
These bioconcentration factors are considerably lower than vahres considered indicative of bioaccumulative
“compounds’of
concern” by the U.S. EPA. Acute toxicity tests using saltwater and fiesbwater algae,
invertebrates and fish have shown BPA to be “slightly to moderately” toxic. Available data suggest “an absence
of chronicity” of BPA in fish. Measured chronic aquatic toxicity data support this observation; however, all
measured exposure values are less than the range of measured and calculated chronic toxicity vahres.
Overall, ah available data show that BPAk rarely detected in surface waters, all calculated and measured
concentrations iu surke
waters are low, is rapidly biodegraded in the environment, has low potential for
bioaccumulation, and all measured and calculated concentrations are lower than all acute or chronic aquatic
toxicity effects by one-to eight-orders of magnitude.
ACKNOWLEDGEMENTS
This work was supported by the Society of the Plastics Industry, Inc.‘s Bisphenol A Task Group and its
member companies, which inch&s Arkaech Chemical Corporation, Bayer Corporation, The Dow Chemical
Company, and Shell Chemical Company.
2170
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