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 REFERENCES 1. AIexam&,H.C.,D.C.DiU,L.W.Smith,P.D.Gu&y,audP.B.Dom. 1988.BisphenoIA:AcuteAquatic Toxicity. 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