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Chemosphere, Vol. 36, No. 10, pp.

2149-2173, 1998
Pergamon Q 1998 Eisevier Science Ltd
All rights r&xnd priacd in Great Britain
0045-6535198 $19.00+0.00
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 product is &red and dried. The second is similar, but uaes
di&mmt malyats and puriktkm 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 other
~andproduas~~chaing~Imlordia&hertn&aswenas~~orother
releases.

H3C CH3

Figurel.Molecular-of A @PA).
2151

Review ofBPA Fate, Eflpectr amiEpa_wre

~~thepateasirlreleasestotheenvimnmmt,theIlkinwtl?~emd~ofBPAwereexrmined. The
obje&ves oftbis study were to mview, a) available data on the physical chara&&tics and remval me&a&ms
that control the di&bution and tie of BPA in the emvirm, 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, prills or flakes. While BPA is molten at
elevated temperatures during mauuthctu@ (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 a v&e of 3.82 using various
ammptkm 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

Puometer Value 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
Boiling Point 22OC(at4mmHg) WI
398 C (at 760 mm Hg) El41

Melting Point HO-155 c I281


157 c 1141

PG 9.59, 10.2 1321


11.30 I561

Water Sobbil@@ 120,000 pglL VI


300,000 pgL I21

Vapor Pressure* 4.OE-8 mm Hg I281


3.96E-7 mm I-Q P41
8.7OErlO mmHjj I21
3.96B9 mm Hg [21

* 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 or as is the
case in saltwater, the expected bioconcentration potential of BPA would be less than predicted with
undisassociated BPA uuder acidic pH conditions.

Table 2. Partitioning Cbara&risties for Bispbenol A.

Parameter Value Comment Reference


Log Kow 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
Log Koc for soil ‘314 (dimensionless) calculated from sohMity WI
and sediment 1524 calculated from log Kow WI
Bioconcentration 5.1-13.8 (dimensionless) measured, 42 da, 150 pg/L ]411
Factor (BCF) <20-68 measured, 42 da, 15 pg/L 1411
42 calculated from solubility WI
196 calculated from log Kow=3.32 Lw
Henrys Constant 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

Atleast17testshavebeenperhmodmeasuringthebiotraatrbilityaud ofBPA us&a

closed bottles, some type of inoculum, and that measured the loss of parrmt BPA, oxygen consuqth, or
production of COP Achievement of 100% reduction ia ThOD is essuhlly equhht to 100%
of oxidizsble par& compound. CoIktively, the data attest to the rqid biodegradatk ofBPA iu s&k w&m
and wastewater -t 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 sys@nsandinstudkthatsimulatewastetre&ment.
‘Ihe “i&rent” bh@ad&@ 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
Table 3. Biologically Mediated Degradation and Chemical Treatment of Biaphenol A.

Endpoint.(a)
Study Type ReSUlta Reference
MUSlWed

U.S. EPA test (similar to co* production 83.6% of ThCO* produced ia 28 days; [421
OECD method 30 1B BPA was “readily” biodegradable
Modified Sturm Test)

Mauometric respirometry 02 consumption 81.1 to 93.1% Oz ummmption and 76.3 to 90.6% TWO, 1251
(OECD method 301F) and CO2 production production in 28 days, 10 day time limit met;
BPA was “readily” biodegradable

Bioohemical Oxygen BOD, BOD, = 71% of ThOD P31


Demand (BOD) BPA was “readily” biodegradable

Closed Bottle Test and BPA oxidation and no oxidation of BPA in Closed Bottle Test, insufkient 1521
Modified Storm Test co* production degradation in mod&d &u-m Test; BPA did not meet
“ready” biodegradability criteria in these two tests

Primary efhlent seed: t,,=3.0 da 1111


biodegradation receivhg stream seed: t,,=2.5 da
River DieAway Houston Ship charmel seed: t,=4.0 days;
overall, 36% loss of BPA in 3 to 5 days with acclimated
microbial populations, BPA was “readily” biodegradable

wastewater -Biolopical
wastewster treatment primary decant pond at plant: 46.9 ppm BPA distribution box: 8.8 [481
efficiency biodegradation ppq outfall: <0.05-0.08 ppm BPA, overall reduction of
>99.8% BPA
Table 3. Biologically Mediated Degradation and Chemical Treatment of Bisphenol A (cant).

Studv TvDe EndDoinffs) Measured Results Reference

BOD and COD removal of BPA 72% COD removal in 24 br, 57% BOD removal in 24 hr; BPA “easily 137,381
decomposed” by acclimated treatment kilities
Extended aeration, activated primary biodegradation inhent and eflhent measured, >92%->96% removal of BPA WI
shxlge system

Biotreatmtmt of BPA- primary biodegradation activated shulge treatment with populations acclimated after 14-da, [231
containiug wastewater >99% removal achieved, >87.5% COD removal in 14-da

30-d modikd SCAS Assay aerobic biodegradation 87-95% aerobic degradation in 30 days, BPA “inherently biodegradable” [531
_ fiio&

Wastewater treatment reduction of BPA in electrochemical oxidation with high NaCl and iaitial pm 10; only simple PI
mehod study wastewater short-chain aliphatic acids were left
Recovery &kiency of BPA removal and recovery of pH neutrahtion, &ration of prwitates, XAD resin absorption of [lOI
fkom wastes BPA BPA fkom clari6ed water; >85% removal of BPA possible
Wastewater treatment reduction of BPA in chemical/physical pretreatnxmt followed by anaerobic biotreatment 1471
method study wastewater .succes@Uy removed BPA in waste
2157

and >87.5% of the COD in two weeks [23]. Jn a study of the e&iency of the fMity wa@ewatert.reat.ment
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 ficil$+s
e&z&, the &ili@+s mceiviq 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]. Biodegradation


tests that were carried out for 30 days by Funm [23], showed exteaudve deg&ation 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 wastewater achieve costly high levels of
biodegradation. 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. The major pathway produced two primary metabolites, 4-hydroxyaceteph~one and 4-
hydrom 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 may photo@ze in surf&e
wateqaswenrstbeatmosphere.speciticexte&ofphotolysiEinWteris on w&r conditions (pq
turbidity, watertlnI&We, and others) and the amom& of 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 photo&&s.

deaivrtive of BPA [28]. Howmd [28]-S&W thatpboW&&tkmofBPAiuwateswouMhsvekalf-lives


of66hrto 16Odaysmtdthat&boxne8pAmsybeve h&&es ofo.74-7.4 hr.
2159

Pm&tedE Llistrihtim of BPA

Dis@utionofBPAiuthe -twasest&tedu??&theMackayI&vel1&gacitymodolitlg
approach [36]. Fug* 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. Ev&ative - models such as Mackay Level 1 allow tho e&n&m of relative
distriis 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 as was the perceatrge of total
moles in each compartment. &gradation 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


solids

Sediment 2.1E+4 2400 22.98 23

Total-100 moles Total=lOO%


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& eqmed. The
di&&&ms cakulated here demon&rate the tendency of BPA that enters the ekmmmt 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 u&g two
&z&water Pseudomoms spcks. A study by Febig [22] u&g PseW puti& rqwti a~ l&hEC, of
>320,OOO&L.,baaedonthe~ofa IO%decreamincellgrowth. StoneaudW [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
&. Ihe 9&h duxmic NOEC for this study was 1170 &. For studies with the saltwater algae SkeIeronenta
cm, 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 &, based on
cell growth, using Selanartrum cqtwicomutum.
2161

Table 5. Aquatic Toxicity Studies for Bisphenol A.

Results
Organism F/M Test Type Endpoint Reference
Cl&L)

F 18-k FJC,, 10% lass gmP&l >320,000 WI


Pseuiomomvjluore.wens F lC,O growth inhibition 54,500 WI

Selmraptrumcapricornutum F %kEC, cell count 2700 Ul


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

-tee

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
NOEC

Mysid ekimp M)ddojnic bahta M 96-k LC,, mat&y 1100 PI

u&

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 mykiw F 96-k LC,, mentality 4ooo r451


Lake Emerald Shiner F 72-k LC,, m&&y 4ooo-6ooo PI

Msdaks Oqzia~ lohpes F 48-k L’& motility 15,ooo [411

Atlsntic shide Menidia menkiia M %k LC,, mortality 9400 VI

Sheqhd minnow Cyprinodon M 96-k LC,, mmtality 7500 [161


variegafus

Note: F/M refers to fieshwster or marine species.


2162

Invertebrates

neto~ofthe~wateriav~~~wasexrmiaedbyAlexrader [I] who reported


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, of
4600 & 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 was not iudkted [ 191. Maud Phil [46] repoxted a 96-h LC,,
of 3ooO-3500 & 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 [l]. No o&x details of the test were


provided. Researchers from the Chemical Inspection and Testiag ktitute 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 *Invert-h5h


OInvext-marine *Fish-fresh 0 Fish - marine
rlvliaobes ): AlgaeNOEC * Invert-NOEC

Figure 2. Toxicity of Bispbenol A to Aquatic Organkms across ‘lkophic Levels.

myaid &imp ibfjs*is 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
trout Oncm~h vykiss were dightly more semitive than the saltwater sbeepsbead mirmow Cyprimxkwz

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, tbe acute toxicity (96-h EC,)
of the green alga Selenaptrwn capric~tum ranged from 2500 to 3 100 @L., while the cluonic 9&h NOEC
was 1170 & 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 Concon@ at Low .Blow (TQ2Q)uf BPA


Rakviag W8ten1 or POTWs (Ibed on 1993 TIU Reports).

Relea8e Receiving streamLow Flow rn4tream concentration


rt Low
FIlCiliQ
O#H V=) 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 lOpmoe&@ 1627 hg BPAmJoases to mrir&e


waters(47%ofthetotalrepo@dby 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~& it is useful
to &t&e 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 kput. Usblg PB-LCYMS, BPAwaa iUtlWdKZ&VO s

at25,&Land8&L,respectively, butwasnotdemoteduaing 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 WI
md pristine waters, 1970s 0.06-O. 11 @IL (n=4) thea between 19741978;

Tokyo, Japan 1.9 /.Jg/L (n=l) alI@WJdWithGChfS

Tama River, Japan 1973 co.01 /@L (Hz); 2rhm3iuilldwtrialueas; 1391


3rd sample was between smple plqmtion techniques
0.01-0.09 crgn not spccifi6d,Gc/Msused

Fiaisheddrinking 1990 not detected (ND) by any 500 liter sample conect~, [91
water an@tkal method malyzed with PB-L4YMS and

GCNS.

vwioustbluae 1996 15 upstreamand 15 WI


w8tersin
U.S. 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 were all low, with most values

nonWed. Measured mrfiwe water con-s (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”, so an application &or of 10 was used to
calculate potential chronic toxicity vahw from acute v&es [19]. Chronic toxicity v&q there&e, are
cozwrhvely 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 is
shown in Figure 3. Measured and predicted BPA exposure wn~tion 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 difkwx between the di&b&ms of
exposure data and the estimated chronic values.
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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