(6) “Biologic Effects of Atmospheric Pollutants—Particulate Poly- (10) Nau, C. A.. Neal. -J.. Stembridge, V., Arch. Ind.
dge, V., Arch. Ind. Hyg., 17,
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21
cyclic Organic Matter’’. National Academy of Sciences, Washing-
ton, D.C., 1972.
(7) Strup, P. E., Giammar, R. D., Stanford, T. B., -Jones, P. W., in
“Carcinogenesis—A Comprehensive Survey", Freudenthal, R. I.,
-Jones, P., Eds., Raven Press, New York, 1976, pp 241-51.
(8) Nau, C. A., paper presented at the Conference on Environmental
Aspects of Chemical Use in Rubber Processing Operations, Akron,
Ohio, March 12-14, 1975.
(9) Neal, J., Thornton, M., Nau. C. A., Arch. Environ. Health, 4,46
(1962).
An Environmental Safety Assessment of Butyl Benzyl Phthalate
William E. Gledhill*, Robert G. Kaley, William J. Adams, Orville Hicks, Paul R. Michael, and Victor W. Saeger
Monsanto Company, 800 N. Lindbergh Boulevard, St. Louis, Mo. 63166
Gerald A. LeBlanc
EG&G Bionomics, Wareham, Mass. 02571
The current environmental safety assessment concludes
that, under present use/disposal patterns, butyl benzyl
phthalate (BBP) does not constitute a hazard to the aquatic
environment. BBP is relatively insoluble in water and tends
to partition to soil, sediment, and biota in the aqueous envi-
ronment. Biodegradation, the controlling rate process for
environmental degradation of BBP, is rapid and extensive in
natural water and sewage systems. Environmental levels of
BBP averaged less than 1 µg/L in water and less than 100 ng/g
in sediment. BBP is acutely toxic to a variety of algae, inver-
tebrates, and fish in the 0.5-5 mg/L range and chronically
toxic to Daphnia and fathead minnows in the 0.1-0.8 mg/L
range. A bioconcentration study indicated that BBP was not
an accumulative or persistent chemical in fish. Comparison
of mean environmental water concentrations of BBP to lab-
oratory chronic toxicity values for Daphnia and fathead
minnows showed an average safety margin of approximately
three orders of magnitude.
Butyl benzyl phthalate (BBP), manufactured by Monsanto
0
COCH2CH2CH2CH3
under the trade name Santicizer® 160, is produced in excess
of 100 X 106 lb annually and is used primarily to plasticize, or
flexibilize, synthetic resins, chiefly poly(vinyl chloride) (PVC).
The major use of BBP is in the production of flooring mate-
rials with smaller amounts also occurring in other household
products. The functionality of BBP results from its high
compatibility with PVC and other resin systems and is at-
tributable to BBP’s unique molecular structure. The polar
carbonyl and aromatic groups interact strongly with polar
chloromethine groups of PVC and the various oxygen-con-
taining functional groups of cellulosic and acrylic resins. The
alkyl group of BBP contributes to the flexibility and resistance
to aqueous extractability of plasticized resins.
The environmental safety of phthalate esters has recently
drawn national attention as a result of the 1976 Consent De-
cree settlement of a lawsuit by the Natural Resources Defense
Council (NRDC) et al. against the Environmental Protection
Agency (EPA) over implementation of the Federal Water
Pollution Control Act. This action resulted in the designation
0013-936X/80/0914-0301$01.00/0 © 1980 American Chemical Society
(1958).
(11) Nau, C. A.. Neal, J., Stembridge, V., Arch. Ind. Hyg., 18, 511
(1958).
(12) Nau. C. A., Neal, J.. Stembridge, V., Arch. Ind. Hyg., 20, 512
(1960).
(13) Nau, C. A., Neal, -J., Stembridge, V., Cooley, R. N., Arch. Envi-
ron. Hyg., 4, 415 (1962).
Received for review October 22, 1979. Accepted December 10,
1979.
of ten classes of chemicals, including alkyl phthalates, by the
Interagency Testing Committee (J) as materials needing
priority testing. The Clean Water Act (CWA) of 1977 trans-
lated much of the Consent Decree into statutory law. Both the
EPA-NRDC Consent Decree and the CWA specifically re-
quire that water quality criteria be established for phthalate
esters. In meeting these requirements the EPA has initially
selected six phthalate esters, one of which is BBP, on which
to develop criteria.
Currently, insufficient published information is available
to make an adequate safety evaluation of BBP. Opportunity
exists for the release of BBP to the environment from manu-
facture, distribution, PVC blending operations, and consumer
use of finished products. However, because of the low rate of
diffusion of BBP from consumer products (2), we believe only
a small percentage of the BBP produced actually enters the
environment. This research project was designed to evaluate
the environmental safety of BBP. Results of both laboratory
and field studies will be described. The current assessment
will not address human health or wildlife effects. Phthalate
esters are readily metabolized in mammalian systems and
show low toxicity in acute, subacute, and chronic feeding
studies (.3).
Experimental
Materials. Commercial grade BBP was used throughout
these studies, except for the microcosm study which used
carbonyl-14C-labeled BBP (specific activity of 6.35 pCi/g).
Both products were synthesized by Monsanto Company.
Purified water for aqueous solubility, octanol/water partition
coefficient, soil adsorption, and photodegradation studies was
obtained from a Milli-Q water purification system (Millipore
Corp., Bedford, Mass.). Pesticide grade organic solvents were
used for all extractions and dilutions.
Analytical Methods. Extraction of the aqueous samples
from the mobility tests involved addition of 10.0 mL of the
centrifuged solution to a 4-dram vial along with 1.0 mL of
hexane. The vial was sealed with an aluminum foil lined cap
and shaken for 2 min. Extraction of water from the environ-
mental samples was accomplished with three 100-mL aliquots
of methylene chloride. Extracts were passed through a 1-in.
layer of NaCl and a 2-in. layer of Na2S04 and concentrated
in a Kuderna-Danish evaporative concentrator. Sediment
samples were homogenized before extraction. A 10-g aliquot
(wet weight) was supplemented with 30 g of Na2S04 to absorb
excess moisture and extracted in triplicate with 50 mL of
methylene chloride using a Polytron® Ultrasonic Homogenizer
Volume 14, Number 3, March 1980 301
 (Brinkman Instrument Co.). Extracts were combined and
concentrated prior to analysis.
Concentrated extracts from laboratory studies were ana-
lyzed by gas chromatography using a Hewlett-Packard 5730
chromatograph equipped with a flame ionization or elec-
tron-capture detector. Samples were injected onto a 1 m or 2
m X 3 mm i.d. glass column packed with 3% OV-101 on
100/120 Gas-Chrom Q (column temperature 230 °C). Con-
centrated extracts from the environmental sampling study
were analyzed by means of a Hewlett-Packard 5982A gas
chromatography/mass spectrometry system with a 5934A data
system in the selected ion monitoring mode. The column was
programmed from 100 to 290 °C at 16 °C/min, and m/e 91 and
149 were monitored at ions characteristic of BBP.
The methods were validated by dosing known amounts of
BBP into water and sediment samples at two concentrations
each. The percent recovery for water dosed at 2 and 10/ug/L
averaged 104.6% (96-112%). Recovery for sediment dosed at
0.2 and 1.0 gg/g averaged 92.3% (86-100%).
Mobility Tests. Aqueous solubility was determined by
slowly stirring 1 mL of BBP with 500 mL of water in an en-
closed container at ambient temperature (20 ± 2 °C). The
aqueous phase was sampled over a period of 3 weeks until
equilibrium was reached. Preparation of samples for gas
chromatographic analysis and the methodology for deter-
mining the octanol/water partition coefficient have been de-
scribed previously (4). The bioconcentration factor for rain-
bow trout was calculated from the partition coefficient using
the equation of Neely et al. (5).
The soil adsorption study was conducted using a batch
technique similar to that recommended by the Environmental
Protection Agency for the premanufacture testing of new
chemical substances (6, p 16257). Three different soils were
used with organic matter ranging from 1.2 to 3.4%. BBP was
added as a concentrated methanol solution to give an initial
concentration in water ranging from 0 to 1 mg/L- Water/soil
mixtures were shaken for 24 h and then centrifuged. The
aqueous phase was analyzed for BBP, and the amount ad-
sorbed to the soil was calculated by difference. The soil par-
tition coefficient was calculated as the ration of BBP adsorbed
to the soil to that remaining in the water.
Persistence Tests. Biodegradation Screening. The
semicontinuous activated sludge (SCAS), carbon dioxide
evolution, and river die-away (RDA) methods were those
described by Saeger and Tucker (7). Anaerobic biodegrada-
tion was assessed using the procedure of Healy and Young (8)
and modifications described by Gledhill (9).
Photodegradation. The general procedure followed in the
photodegradation screening is similar to that described by the
EPA (6, p 16271) using sunlight exposure to aqueous solutions
of BBP in sealed tubes. The tubes used in the study were
13-mm o.d. quartz tubes reduced to a short section of 8-mm
tubing at the open end. The overall volume of the tubes was
about 11 mL. The tubes were sealed with Chemplast Taper-
Tite Teflon connectors and short lengths of 8-mm glass rod.
A platform capable of holding 132 tubes was constructed from
three 6-ft lengths of aluminum bar stock (1 in. X 0.5 in.).
Tubes were positioned on the bar at a 60° angle to the ho-
rizon.
For the study, 14 tubes were filled with 10 mL of a 1-mg/L
BBP solution. The tubes were analyzed in duplicate according
to the following sunlight exposure schedule: 0, 2, 4,10,17, and
28 days. Two tubes, wrapped in black polyethylene film,
served as dark controls and were analyzed at the last sampling
point. For analysis, 1 mL of hexane was pipetted quantita-
tively into the tube. A 20-mm o.d. glass bulb (approximate
volume of 15 mL) with a section of 8-mm tubing at the open
end was tightly connected to the quartz tube. The aqueous
solution and hexane were shaken down into the larger bulb.
302 Environmental Science & Technology
After the mixture was vigorously shaken for 1 min, it was re-
turned to the quartz tube where the phases were allowed to
separate. The quartz tube was then tightly stoppered and
refrigerated until the appropriate time for GC analysis of the
hexane phase.
The sunlight exposures took place in St. Louis on the 28
days between August 20 and September 17, 1979.
Microcosm. A microcosm simulating a lake environment
was constructed using a 5-gal aquarium and the core-chamber
technique described by Bourquin et al. (10). Water and
sediment were collected from the littoral region of a spring-fed
freshwater lake (Lake 34, Busch Wildlife Area, St. Charles
County, Mo.). The sediment was screened through a steel
screen (0.5-in. mesh) to remove large particulates. The bottom
of the aquarium was covered with a Vs-in. Teflon sheet fitted
with 8 evenly spaced No. 7 silicone stoppers. Four liters of
sediment and 12 L of lake water were then added to the
aquarium. The microcosm was then allowed to stabilize for
a period of 6 weeks with gentle aeration and a 16/8 h light/dark
cycle using 300-ft-c GE Daylight fluorescent lights.
At the end of the stabilization period, the core chambers
were created by inserting eight sterile glass cylinders (3.8 X
30 cm) through the water column and sediment onto the sili-
cone stoppers. A Plexiglas template covering the top of the
aquarium served as a guide for the coring process. Each
chamber contained about 110 mL of lake water and 35 cm3 of
sediment. Gas manifolds supplied either CC>2-free air or
oxygen-free nitrogen just beneath the surface of each chamber.
Gas flow was regulated by means of aquarium valves. Exhaust
gas was passed through a Tenax-GC resin trap to remove
volatilized organics and then through a CO2 scrubbing system
containing 10 mL of 2-methoxyethanol-monoethanolamine
solution (7:1, v/v).
14C-labeled BBP was added to the core chamber as an ac-
etone solution (0.11 mg of BBP/20 pL of acetone) resulting
in a final concentration of 1 mg/L. Samples of the water col-
umn were removed at 0, 3, 7,14, 21, and 28 days and analyzed
for residual BBP and radioactivity. Ethanolamine traps were
replaced according to the same schedule and the scrubber
solutions were assayed for radioactivity. Tenax traps were
removed at the end of the 28-day test and eluted with acetone.
Eluates were then assayed for radioactivity.
Environmental Sampling. Water and sediment samples
were obtained during November 1977 and May 1978 from
various industrialized and nonindustrialized locations (Table
I). Water samples (900 mL), except those from San Francisco
Bay, were drawn through a 50-ft Teflon tube into 1-L glass
bottles by means of a 12-V vacuum pump. The Teflon line was
cleaned with acetone between sampling stations. The water
column was sampled by raising the Teflon line at a constant
rate from the bottom to the surface while the pump was op-
erating. At least three and usually five samples were collected
at each location. The samples were collected in a straight-line
traverse across each river and harbor. San Francisco Bay
samples were grab samples of surface waters at five locations.
Sample bottles containing 100 mL of methylene chloride were
sealed with an aluminum foil lined cap and shaken for 1 min
in the field to extract and preserve the BBP.
Sediment samples (100 g) were obtained with Ponar and
Student-Ekman grab samplers. Three samples were taken
from both sides and the middle of each river and harbor,
wrapped in aluminum foil, placed in polyethylene containers,
and stored on dry ice. They were subsequently transferred to
a freezer (-10 °F) and stored until analyzed.
Aquatic Toxicity Tests. Acute Lethality. Static acute
toxicity tests were conducted with algae (Dunaliella tert-
iolecta, Microcystis aeruginosa, Navícula pediculosa, Sele-
nastrum capricornutum, Skeletonema costatum), water fleas
(Daphnia magna), mysid shrimp (Mysidopsis bahía), fathead
Table I. Residues of BBP in Natural Water and Table II. Parameters to Assess the Environmental
Sediments Mobility of Butyl Benzyl Phthalate
av BBP concna 6
vapor pressure, 20 °C 8.6 X 10 mmHg
collection water,b sediment,
location date Mg/L ng/g vapor pressure, 200 °C 1.9 mmHg
aqueous solubility, deionized water 2.9 ± 1.2 mg/L
Waukegan Harbor, III. 11/8/77 0.25 N.D.
octanol/water partition coefficient 5.9 ± 4.3 X 104
(5/2)d (3/0)
11/8/77 0.23 N.D. calculated bioconcentration factor 510
Waukegan Creek, III.
(5/3) (3/0) soil adsorption coefficient, measured3 68-350
Upper Saginaw River, 11/10/77 0.43 567 a
Measured at 20 ± 2 °C.
Saginaw, Mich. (3/3) (3/3)
Lower Saginaw River, 11/10/77 0.43 400
Bay City, Mich. (4/4) (3/3)
Illinois River, Grafton, III. •
11/14/77 0.47 N.D. LC50 is stated as being greater than the highest concentration
(4/3) (3/0) tested.
Meramec River, 11/14/77 0.38 N.D. Chronic Toxicity. A two-generation water flea chronic
Times Beach, Mo. (4/4) (3/0) study was conducted following the procedure of Macek et al.
Missouri River, 11/16/77 0.2 N.D. (16). The diluent water consisted of deionized well water re-
St. Louis, Mo. (3/2) (3/0) constituted to a hardness of 175 ± 15 mg/L, an alkalinity of
Missouri River, 11/16/77 0.25 100 115 ± 10 mg/L, a pH of 8.1 ± 0.2, and a specific conductance
Weldon Springs, Mo. (4/4) (4/1) of 600 ± 100 µ -1. The dissolved oxygen remained above 60%
Mississippi River 11/30/77 0.30 of saturation throughout the study. A Mount and Brungs (17)
North St. Louis, Mo. 5/23/78 (8/3) proportional diluter delivered water and chemical for five
Mississippi River 11/30/77 2.4 N.D.
exposure levels, a control, and a solvent control. The maxi-
South St. Louis, Mo. 5/23/78 (8/7) (3/0) mum amount of solvent used was 0.1 mL/L of dimethyl-
San Francisco Bay N.D.
formamide! All treatments and controls were conducted in
(5 sites) (5/0)
b
quadruplicate. Test solutions were delivered to the aquaria
a
Average concentration of those samples containing BBP. Detection limit at a rate of four replacement volumes per day. Test chambers
0.2 mq/L. c Detection limit 100 ng/g. d Number of samples analyzed/number were 2-L battery jars with a Nitex screen covering a 3 X 8 cm
of samples containing measurable levels of BBP.
notch on the upper edge of the jar to retain the water fleas.
Twenty water fleas (24 h old) were placed in each test cham-
ber. Survival and reproduction were monitored on day 7 and
minnows (Pimephales promelas), bluegills (Lepomis ma- on all weekdays thereafter for the duration of the two 21-day
crochirus), rainbow trout (Salmo gairdnerii), and sheepshead exposures. On day 21, all adults were removed, 20 offspring
minnows (Cyprinodon variegatus). Phytotoxicitv tests fol- were left in the test chambers, and the second generation
lowed the EPA algal assay procedure (11). All acute toxicity- study was started. The water fleas were fed 1 mL of a Selen-
tests followed the methods recommended for standardized astrum capricornutum suspension (8-30 X 106 cells/mL) once
laboratory toxicity tests (12). a day and 1 mL of a Strike fish food suspension (5.5 mg/mL)
Waterflea tests were conducted in lake water at 23 °C three times a day.
(hardness, 110 mg/L; alkalinity, 102 mg/L; pH 7.8). Units for Water samples were collected for BBP analysis at the ini-
hardness and alkalinity, mg/L, are actually expressed as mg/L tiation of the study and once a week thereafter from two
as CaCOs- Rainbow trout, fathead minnows, and bluegills were replicates at each treatment level. The mean measured con-
tested in reconstituted soft water (hardness, 40 mg/L; alka- centrations were 73.8% of nominal. The average (±1 SD) test
linity, 32 mg/L; pH 7.5) at 12 and 22 °C, respectively. Fathead concentrations were <0.01, <0.01, 0.035 (0.008), 0.058 (0.019),
minnows were also tested at a water hardness of 160 mg/L. 0.099 (0.035), 0.26 (0.05), and 0.76 (0.17) mg/L.
Tests with mysid shrimp and sheepshead minnows were
conducted at 20 °C in natural seawater having salinities of 18 Results and Discussion
and 24 g/L, respectively. Environmental Mobility. Table II summarizes key
Time-Independent Toxicity. A time-independent flow- physical/chemical properties used to assess the likely move-
through study with fathead minnows was conducted for 14 ment of butyl benzyl phthalate in the environment. U.S.
days in well water (hardness, 295 mg/L; alkalinity, 304 mg/L; production in 1978 was in excess of 100 X 106 lb. Vapor pres-
pH 8.1; temperature 22 ± 1 °C (dissolved oxygen, 60% satu- sure measurements at ambient temperature indicate a low
ration)). A continuous flow delivery system (13) with a peri- tendency for atmospheric transport. However, at 200 °C, a
staltic pump was used to deliver the water and chemical for temperature which is approached in the formulation of con-
five exposure levels, a control, and a solvent control. A con- sumer products, volatility is high and may offer a mechanism
stant amount of solvent (0.33 mL/L of dimethylformamide) for release of some BBP to the environment. BBP has mod-
was delivered to all test aquaria except the control. The test erately low water solubility and, consequently, would be ex-
tanks were all-glass aquaria containing 15 L of test solution. pected to partition to solids (soil, sediment, and biota) in
Thirty fish (average weight 0.88 g) per aquarium were tested. natural environments. Octanol/water and soil partition
A water flow rate of 6 L/h was maintained during the study coefficients also support the view that BBP has a moderate
period. Water samples for BBP analysis were collected five potential to adsorb to soil and accumulate in fish.
times during the study. The mean measured concentrations Environmental Persistence. The persistence of a chem-
were 88.3% of nominal. The average (±1 SD) concentrations ical is related to its susceptibility to biological, chemical, and
in the seven test aquaria were <0.01, <0.01, 0.74 (0.22), 1.06 photochemical processes in nature. Persistence studies (Table
(0.29), 2.10 (0.27), 2.77 (0.45), and 3.23 (0.80) mg/L. III) indicate biodegradation to be the key rate process for
All LCso and EC50 values and their 95% confidence limits destruction of BBP in the environment. Biodegradation
were calculated using the method of Litchfield and Wilcoxon screening studies indicate BBP undergoes both substantial
(14) or moving average angle analysis (15). In tests where less primary biodegradation (i.e., the disappearance of the parent
than half the organisms died in the highest concentration, the molecule) in activated sludge and river water, and ultimate

Volume 14, Number 3, March 1980 303

Table III. Environmental Persistence of Butyl Benzyl Table IV. Acute Lethality of BBP, Measured in Static
Phthalate Tests, to Several Species of Algae, Invertebrates, and
Fish
half-life,
persistence primary3 ultimate6 days days 96-h EC50 95% no effect
or LCso> confidence concn,
biodegradation species mg/L interval, mg/L mg/L
activated sludge 93-99 1
algae3
CO2 evolution, 96 28 1000 560
Microcystis
aerobic
Dunaliella 1.0 0.2-5 0.3
gas production, <10 28
Navícula 0.6 0.2-2 0.3
anaerobic
Skeletonema 0.6 0.3-2 0.1
river water 100 9 2
Selenastrum 0.4 0.2-1 0.1
lake water micro- >95 7 <4
cosm invertebrates
lake water micro- 51-65 28 Daphnia magnab 3.7 3.0-4.6 1.0
cosm mysid shrimp 0.9 I
N> 0.4
photodegradation <5 28 >100 fish
chemical degradation <5 28 >100 fathead minnow c 5.3 4.3-6.5 2.2
(hydrolysis) fathead minnow d 2.1 1.7-2.5 1.0
3 b
Disappearance of BBP as measured by gas chromatography. Minerali- bluegill 1.7 1.0-2.8 0.36
zation under aerobic conditions to CO2, under anaerobic conditions to H2, CH4, rainbow trout 3.3 2.9-3.9 <0.36
and CO2· 2.4-3.9
sheepshead minnow 3.0 1.0
3 6 3
LC50 based on cell counts. 48-h EC50. 160 mg/L hardness as CaC03.
d
40 mg/L hardness as CaC03.
biodegradation (i.e., mineralization to inorganic components)
in a CO2 evolution test. BBP was not significantly biodegraded
in an anaerobic test system. BBP does not appear to be sus- signing an arbitrary value of 100 ng/g to those samples not
ceptible to direct photolysis. Our initial screening in Pyrex containing measurable BBP results in a geometric mean
tubes had shown evidence of direct photolysis, but a repeat concentration of 136 ng/g BBP for the sediments analyzed.
of the test using the procedure described showed no significant The monitoring studies thus support the laboratory per-
decrease in the BBP concentration in either the light-exposed sistence studies and indicate that BBP does not occur at high
samples or dark controls. levels in the natural environment. As with many large-volume
Detailed hydrolysis studies were not conducted on BBP. commercial or natural products, levels which are observed
Based on the results with the photolysis dark controls, hy- probably result from continual input of BBP to the system.
drolysis does not appear to be a major degradation pathway. It is also interesting to note that the monitoring studies sup-
This is in general agreement with the data of Wolfe (18) who port the laboratory mobility studies. Adsorption coefficients
found hydrolytic half-lives ranging from 80 to 4000 days for calculated from both the ratio of the mean and geometric
a series of dialkyl phthalate esters at pH 8 and 30 °C (4). mean sediment concentrations of BBP to the water concen-
In a lake water-sediment microcosm, more closely simu- trations (428/0.75 and 136/0.35) equal 571 and 389, respec-
lating a “real-world” environmental compartment, car- tively. These are in close agreement with the measured soil
bonyl- 14C -labeled BBP rapidly disappeared from the aqueous adsorption coefficients of 68-350.
phase. At an initial concentration of 1 mg/L in replicate core Aquatic Toxicity. Acute Lethality. Four species of fish
chambers within the microcosm, the half-life of BBP was 2-4 and Daphnia magna were equally susceptible to butyl benzyl
days. After 7 days, greater than 95% removal of BBP from the phthalate (Table IV). Based on 96-h LC50 values, algae were
water column was observed, and 28-49% of the label was the most sensitive species. An exception to this was the
evolved as 14C02. At the conclusion of the 28-day study, blue-green alga, Microcystis aeruginosa, which was very re-
51-65% of the label was converted to 14CC>2. The labeled BBP sistant to BBP (LC50 1000 mg/L). LC50 values for mysid
used in this study had a relatively low specific activity and shrimp were intermediate to those for fish and algae.
attempts to characterize soil residues were not undertaken. Time-Independent Toxicity. A time-independent flow-
Higher specific activity BBP is currently being synthesized through study with fathead minnows indicated that BBP was
for a more detailed microcosm study. not an accumulative toxin. The 4- and 14-day LC50 values
The monitoring of domestic wastewater treatment systems (±95% confidence interval) were 2.32 (1.39-3.88) and 2.25
and natural waters away from BBP manufacturing sites has (1.34-3.77) mg/L. The lowest measured concentration where
been conducted. Monitoring of one local domestic activated effects were observed after 14 days of exposure was 1.06 mg/L.
sludge plant showed influent sewage, treated effluent, and With the exception of Microcystis aeruginosa, all LC00 values
aeration lagoon water to contain 8.0,1.3, and 1.0 Mg/L BBP, were within one order of magnitude. This small difference in
respectively. species sensitivity suggests that the variation in the chronic
A more detailed survey of major rivers, Waukegan Harbor, toxicity of BBP to aquatic organisms would also be small.
and San Francisco Bay (Table I) indicated 66% of the water Chronic Toxicity, (a) Invertebrates. Results of a two-gen-
samples analyzed contained low levels of BBP. The samples eration chronic study indicated that BBP was not highly toxic
ranged in concentration from 0.2 to 4.1 Mg/L BBP and aver- to Daphnia magna. Survival was affected only in the second
aged 0.75 Mg/L. These values agree with those reported by generation at the highest test concentration (0.76 mg/L).
Sheldon and Hites (19) for the Delaware River. Assigning an Survival of control organisms averaged 90% in both genera-
arbitrary concentration of 0.2 Mg/L (the limit of detection) to tions. Reproduction was impaired in both generations only
those samples in which BBP was not detected allows calcu- at the highest test concentration. Second generation effects
lation of the geometric mean concentration of 0.35 Mg/L as the were no different than first generation effects. The maximum
average BBP concentration in the surface waters tested. Only acceptable toxicant concentration (MATC) range and corre-
25% of the sediments analyzed contained detectable BBP sponding application factors (chronic toxicity/acute toxicity,
levels and averaged 428 ng/g. As with the water samples, as- 20) were 0.26-0.76 mg/L and 0.07-0.21.

304 Environmental Science & Technology

 (b) Fish. LeBlanc et al. (21) reported the results of a 30-day
post-hatch fathead minnow embryo-larval study with BBP.
The highest measured concentration below which no effects
were observed was 0.36 ± 0.16 mg/L. At 0.36 mg/L, a signifi-
cant (P > 0.05) reduction in growth was seen. Hatchability
and survival were normal. The MATC range and corre-
sponding application factors were 0.14-0.36 mg/L and
0. 06-0.16. These data compare very well with the results of
.the Daphnia magna chronic study.
Bioconcentration. A bioconcentration factor (BCF) of 663
was observed at equilibrium (21 days) in bluegills exposed to
9.73 ± 1.75 Mg/L 14C-labeled BBP (22). The measured value
agrees very wéll with that calculated from the octanol/water
partition coefficient (Table I). Since the measured BCF was
based on 14C determinations and not actual BBP concentra-
tions in fish tissue, the actual BCF might be significantly less
due to metabolism. Mehrle and Mayer (23) reported biocon-
centration factors of 155 to 886 for fathead minnows exposed
to di-2-ethylhexyl phthalate (DEHP) based on 14C analysis,
whereas actual BCF based on analysis of DEHP in tissue
ranged from 33 to 70% less than 14C measurements depending
on the exposure concentration. The depuration half-life for
BBP in bluegills was less than 2 days. These data support the
toxicity results and indicate that BBP is not an accumulative
or persistent chemical.
Environmental Safety Assessment. The basic concepts
of safety assessment (24-26) focus on the environmental fate,
1. e., mobility and persistence, and the ecological effects of a
chemical. The actual assessment of safety is based on the
magnitude of the difference (margin of safety) between the
aqueous environmental exposure concentration and the lowest
observed biological effect on a representative aquatic species.
The greater the margin of safety (safety factor) the more
confidence there is that production, use, and disposal of a
given chemical will not adversely impact the aquatic envi-
ronment.
Further considerations are also necessary. The material, its
impurities, and reaction products should be well enough un-
derstood that ecological surprises are unlikely. Bioconcen-
tration factors should be small enough to suggest that or-
ganisms exposed to concentrations of a chemical in the water
or in their food chain are not adversely affected. There also
should be no long-term environmental sinks where concen-
trations of a chemical might accumulate resulting in delayed
serious problems.
The present data base for BBP is not totally complete;
however, there is sufficient information to assess the aqueous
environmental safety of this chemical. Results of environ-
mental faté testing indicate that BBP is relatively insoluble
in water and will partition to suspended solids and sediment
(Table II). Vapor pressure measurements suggest that parti-
tioning from water to air is not likely. Biodegradation is the
controlling rate process for the environmental degradation
of BBP. Rates of photolysis and hydrolysis appear to be too
slow to significantly alter aqueous environmental concen-
trations of BBP.
The results of our environmental monitoring program
support the conclusion that widespread high concentrations
of BBP are not present in the environment. Levels of BBP in
environmental water and sediment samples were generally
less than 1.0 Mg/L and 100 ng/g, respectively. A few localized
spots contained somewhat higher levels; however, no samples
were analyzed which showed concentrations in the sediment
above 0.7 Mg/g or in water above known chronic effect levels
for aquatic organisms.
Comparison of the geometric mean environmental water
concentration (0.35 Mg/L) to the geometric mean calculated
from the MATC effect/no effect concentration limits for the
water flea (359 Mg/L) and fathead minnow (224 Mg/L) chronic
studies shows an average margin of safety of approximately
three orders of magnitude. A comparison of the highest ob-
served environmental water concentration (4.1 Mg/L) with the
geometric mean MATC value for the fathead embryo-larval
study demonstrates a safety factor in excess of 50.
This current safety assessment concludes that BBP under
its present use and disposal patterns does not constitute a
hazard to the safety and well being of the aquatic environ-
ment.
Acknowledgments
The authors gratefully acknowledge the excellent technical
assistance of D. Busiere, J. A. Dixon, and W. J. Renaudette
throughout the course of the study. Thanks are extended to
R. Parrish of EG&G Bionomics, Pensacola, Fla., for con-
ducting the marine water toxicity studies.
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Received for review June 11, 1979. Accepted December 12, 1979.
Volume 14, Number 3, March 1980 305