vvEPA
United States
Environmental Protection
Agency
Office of Water
Regulations and Standards
Criteria and Standards Division
Washington, DC 20460
EPA 440/5-86O08
August 1988
Ambient
Water Quality
Criteria
for
Aluminum - 1988
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AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA FOR
ALUMINUM
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL RESEARCH LABORATORY
DULUTH, MINNESOTA
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NOTICES
on for ^ ™lcri:iai Planets does not constitute endorsement
NTIS Number - PB88 245 998
11
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FOREWORD
Section 304(a)(l) of the Clean Water Act of 1977 (P i QSJ,,,I
the Administrator of the Environmental Prnr^i A 95~217) requires
quality criteria that accurate^ reflect 1"?7 t0 publlsh "ater
the kind and extent of all idJntiftable
might be expected from the
including ground water
presenc 0 Do
poll
KS°!entlfic knowled««
*"* WClfare that
-
in any body of water,
for the same JoTlutJSi")
,
EPA aquatic life
Watert ul
program impact in each sect on. In
-
sction 3o th a differe"t
? uji»f.f?.':..r!f"css;1:
acceptable pollutant concentrations' in amb T' fnforceable •«!"•
Water quality criteria adopted n Wate" Within that State.
same numerical values a er a
many situations States mi*ht wan?
under section 304 to renfct local
patterns before incorporation i
could have the
o on 304. However, in .
env?ronLn\ ?' qU!Ut7 CriterU d^eloped
°nd'tl°ns and human exposure
-ter-reUted programs of th Agency
°ther
Martha G. Prothro
Director
Office of Water Regulations and Standards
AUG 2 3
111
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ACKNOWLEDGMENTS
Larry T. Brooke
(contributor)
University of Wisconsin-Superior
Superior, Wisconsin
Charles E. Stephan
(document coordinator)
Environmental Research Laboratory
Duluth, Minnesota
i v
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CONTENTS
Page
Foreword ........ . .............
........................................... 111
Acknowledgments ..............
......................................... iv
Tables ....................
Introduction ...........
................................................ 1
Acute Toxicity to Aquatic Animals .....
............................... 4-
Chronic Toxicity to Aquatic Animals ....................
....................... D
Toxicity to Aquatic Plants ............
.................................... 6
Bioaccuroulation ...........................
Other Data ............
.................................................. 7
Unused Data .........
[[[ 8
Summary ...........
[[[ 9
National Criteria. . . .
.................................................. 10
Implementation ........
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TABLES
Page
1. Acute Toxicity of Aluminum to Aquatic Animals 16
2. Chronic Toxicity of Aluminum to Aquatic Animals 19
3. Ranked Genus Mean Acute Values with Species Mean Acute-Chronic
Ratios 21
4. Toxicity of Aluminum to Aquatic Plants 23
5. Bioaccumulation of Aluminum by Aquatic Organisms 24
6. Other Data on Effects of Aluminum on Aquatic Organisms 25
vi
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Introduct i on
The chemistry of aluminum in surface water is complex because of five
properties (Campbell et al. 1983; Hem 1968a,b; Hem and Roberson 1967; Hsu
1968; Roberson and Hem 1969; Smith and Hem 1972). First, it is amphotenc:
it is more soluble in acidic solutions and in basic solutions than in
circumneutral solutions. Second, such ions as chloride, fluoride, nicrate,
phosphate, and sulfate form soluble complexes with aluminum. Third, it can
form strong complexes with fulvic and humic acids. Fourth, hydroxide ions
can connect aluminum ions to form soluble and insoluble polymers. Fifth,
under at least some conditions, solutions of aluminum in water approach
chemical equilibrium rather slowly. This document addresses the toxicity of
aluminum to freshwater organisms in waters in which the pH is between 6.5 and
9.0, because the water quality criterion for pH (U.S. EPA 1976) states that a
pH range of 6.5 to 9.0 appears to adequately protect freshwater fishes and
bottom-dwelling invertebrate fish food organisms from effects of the hydrogen
ion. At a PH between 6.5 and 9.0 in fresh water, aluminum occurs
predominantly as monomeric, dimeric, and polymeric hydroxides and as
complexes with humic acids, phosphate, sulfate, and less common anions. This
document does not contain information concerning the effect of aluminum on
saltwater species because adequate data and resources were not available.
Several investigators have speculated about the toxic form of aluminum.
Freeman and Everhart (1971) found that the toxicity of aluminum increased as
pH increased from 8.8 to 8.99. They concluded that soluble aluminum was the
toxic form. Hunter et al. (1980) observed the same relationship with rainbow
trout over a pH range of 7.0 to 9.0. However, the opposite relationship '
resulted in a study with rainbow trout by Call (1984) and in studies with the
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fathead minnow by Boyd (1979), Call (1984), and Kimball (Manuscript). The
tests conducted by Freeman and Everhart (1971), Hunter et al. (1980), and
Kimball (Manuscript) were all renewal or flow-through and showed the lowest
acute values, whereas the other tests were static. In addition, because the
polymerization of aluminum hydroxide is a relatively slow process the
chemical form of aluminum might have differed from test to test due to the
amount of time the aluminum was in stock and test solutions.
Driscoll et al. (1980) worked with postlarvae of brook trout and white
suckers under slightly acidic conditions and concluded that only inorganic
forms of aluminum were toxic to fish. Hunter et al. (1980) reported that the
toxicity of test solutions was directly related to the concentration of
aluminum that passed through a 0.45 ^m membrane filter. In a study of the
toxicity of "labile" aluminum to a green alga, Chlorella pyrenoidosa.
Helliwell et al. (1983) found that maximum toxicity occurred in the pH range
of 5.8 to 6.2. This is near the pH of minimum solubility of aluminum and
maximum concentration of AMOHJg'*'. They found that the toxicity of
aluminum decreased as pH increased or decreased from about 6.0, and they
speculated that the monovalent hydroxide is the most toxic form. Seip et al.
(1984) stated that "the simple hydroxides (Al(OH)'1'2 and A1(OH)2'1') are
regarded as the most dangerous forms while organically bound Al and polymeric
forms are less toxic or essentially harmless."
In dilute aluminum solutions, formation of particles and the large
insoluble polynuclear complexes known as floe is primarily a function of the
concentrations of organic acids and the hydroxide ion (Snodgrass et al.
1984). Time for particle formation varies from < 1 min. to several days
(Snodgrass et al. 1984) depending upon the source of aluminum, the pH, and
the presence of electrolytes and organic acids. When particles form
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aggregates Urge enough to become visible, the floe is whitish and tends to
settle. Mats have been reported blanketing a stream bed (Hunter et al.
1980). Laboratory studies conducted at alkaline pHs have reported floe in
the exposure chambers (Brooke 1985; Call 1984; Lamb and Bailey 1981; Zarini
et al. 1983). The floe did not appear to affect most aquatic species.
However, the swimming ability of Daphnia ma^na was impeded by "fibers" of
flocculated aluminum trailing from the carapaces, and the movements and
perhaps feeding of midges was affected, ultimately resulting in death (Lamb
and Bailey 1981). Bottom-dwelling organisms might be impacted more by
aluminum floe in the field than in the laboratory.
Aluminum floe might coprecipitate nutrients, suspended material, and
microorganisms. Removal of phosphorus from water has been observed in
laboratory studies (Matheson 1975; Minzoni 1984; Peterson et al. 1974) and in
a lake (Knapp and Soltero 1983). Turbidity due to clay has been removed from
pond waters using aluminum sulfate (Boyd 1979). Unz and Davis (1975)
speculated that aluminum floc might coalesce bacteria and concentrate organic
matter in effluent,, thus assisting the biological sorption of nutrients.
Aluminum sulfate has been used to flocculate algae from water (McGarry 1970;
Minzoni 1984; Zarini et al. 1983).
An understanding of the "Guidelines for Deriving Numerical National Water
Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
(Stephan et al. 1935). hereafter referred to as the Guidelines, and the
response to public comment (U.S. EPA 1985a) is necessary in order to
understand the following text, tables, and calculations. Results of such
intermediate calculations as Species Mean Acute Values are given to four
significant figures to prevent roundoff error in subsequent calculations, not
to reflect the precision of the value. Unless otherwise noted, all
concentrations of aluminum in water reported herein from toxicity and
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bioconcentration tests are expected to be essentially equivalent to
acid-soluble aluminum concentrations. All concentrations are expressed as
aluminum, not as the chemical tested. The latest comprehensive literature
search for information for this document was conducted in July, 1986; some more
recent information was included.
Acute Toxicitv to Aquatic Animals
The earliest study of the toxicity of aluminum to aquatic life was
performed by Thomas (1915) using mummichogs acclimated to fresh water. His
report lacks detail and it is unclear whether the aluminum sulfate was
anhydrous or hydrated. Assuming that the anhydrous form was used, the
calculated concentrations of aluminum where all of the fish died in 1.5 and 5
days were 2,200 and 1,100 fig/l, respectively. More recent tests with fish
showing similar sensitivities to aluminum (Tables 1 and 6) were conducted with
brook trout with a 96-hr LC50 of 3,600 pg/L (Decker and Menendez 1974),
rainbow trout with a 72-hr LC50 of 5,200 pg/L (Freeman and Everhart 1971),
and common carp with a 48-hr LC50 of 4,000 ng/l (Muramoto 1981). Other fish
species tested were more resistant to aluminum.
The range of concentrations of aluminum that was acutely toxic to
freshwater invertebrate species was about the same as the range of
concentrations that was toxic to fish. The lowest acute values for
invertebrates are 1,900 ng/L (McCauley et al. 1986) and 3,690 ng/L (Call
1984) for ceriodaphnids, whereas the highest acute value is
55.500 fig/I in a test with a snail (Call 1984). No data are available
concerning the effect of pH on toxicity of aluminum to invertebrates.
Species Mean Acute Values (Table 1) were calculated as geometric means of
the available acute values, and then Genus Mean Acute Value.8 (Table 3) were
calculated as geometric means of the available Species Mean Acute Values.
Several species tested were not exposed to aluminum concentrations high
4
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enough to allow calculation of an LC50. Although these were ranked in Table
3 according to the highest concentration used in the test, this does not
imply a true ranking of sensitivities. The freshwater Final'Acute Value for
aluminum at a pH between 6.5 and 9.0 was calculated to be 1,496 ^g/L using
the procedure described in the Guidelines and the Genus Mean Acute Values in
Table 3. Because acute values are available for only fourteen genera, the
FAV is about one-half the acute value for the most sensitive genus.
Chronic Tnvicitv to Aquatic Animals
Chronic toxicity values for aluminum have been determined with three
freshwater species (Table 2). McCauley et al. (1986) found that
2.600 ^g/L reduced survival and reproduction of CeriodaphnU dubia by 23%
and 92%, respectively. An aluminum concentration of 1,400 fig/L reduced
survival by 11%. but increased reproduction. Although survival increased at
concentrations above 2,600 pg/L, no reproduction occurred. In a
life-cycle test with Daphnia ma*™, survival was the same at 540 MS/L as
in the control treatment, but was reduced about 29% at 1.020 /jg/L
(Kimball. Manuscript). Reproduction was about the same at 1,020 pg/L as
in the control treatment. Biesinger and Christensen (1972) obtained a 21-day
LC50 of 1.400 ng/L with D. ma^na (Table 6). They estimated that
320 ,if/L would reduce reproduction by 16%. but the concentrations of
aluminum were not measured in the test solutions.
Kimball (Manuscript) reported the results of an early life-stage test
with fathead minnows. An aluminum concentration of 4.700 Mg/L reduced
weight by 11.4%. whereas 2,300 Mg/L reduced weight by 7.1%. Survival at
both concentrations was as good or better than in the control treatment.
These chronic tests indicate that, of the three species tested, the
invertebrates are more sensitive to aluminum than the vertebrate.
5
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The three available acute-chronic ratios for aluminum are 0.9958 with
Oriodaphnia dubia. 51.27 with Daphnia magna, and 10.64 with the fathead
minnow (Table 2). These values follow the common pattern that acutely
sensitive species have lower acute-chronic ratios (Table 3). The Final
Acute-Chronic Ratio is meant to apply to acutely sensitive species, and.
therefore, should be close to 0.9958. However, according to the Guidelines.
the Final Acute-Chronic Ratio cannot be less than 2, because a ratio lower
than 2 would result in the Final Chronic Value exceeding the Criterion
Maximum Concentration. Thus the Final Chronic Value for aluminum is equal to
the Criterion Maximum Concentration of 748.0 ng/L for fresh water at a pH
between 8.5 and 9.0 (Table 3).
Data in Table 6 concerning the toxicity of aluminum to brook trout and
striped bass show that the Final Chronic Value should be lowered to
87 pg/L to protect these two important species. Cleveland et al.
(Manuscript) found that 169 ng/L caused a 24% reduction in the weight of
young brook trout in a 60-day test, whereas 88 A»g/L caused a 4% reduction
in weight. In a 7-day test, 174.4 ^g/L killed 58% of the exposed striped
bass, whereas 87.2 ng/L did not kill any of the exposed organisms (Buckler
et al., Manuscript). Both of these tests were conducted at a pH of 6.5 to
6.6.
Toxicity to Aquatic Plants
Single-celled plants were more sensitive to aluminum than the other
plants tested (Table 4). Growth of the diatom, Cvclotella meneghiniana, was
inhibited at 810 ng/L, and the species died at 6,480 ng/L (Rao and
Subramanian 1982). The green alga. Selenastrum capri cornutum. was about as
sensitive to aluminum as the diatom. Effects were found at concentrations
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ranging from 460 Mg/l (Call 1984) to 990 ng/L (Peterson et al. 1974).
Among multice1lular plants, root weight of Eurasian watermi1foi1 was
significantly decreased at 2,500 Mg/L, but duckweed was not affected at
45,700 ng/l (Table 4). A Final Plant Value, as defined in the Guidelines.
cannot be obtained because no test in which the concentrations of aluminum
were measured and the endpoint was biologically important has been conducted
"i with an important aquatic plant species.
Bi oaccunmlat i on
Cleveland et al. (1986) found that young brook trout contained more
aluminum after exposure for 15 days than after exposure for 30 days, and the
bioconcentration factors ranged from 50 to 231. No U.S. FDA action level or
other maximum acceptable concentration in tissue, as defined in the
Guidelines, is available for aluminum, and, therefore, no Final Residue Value
can be calculated.
Other Data
Additional data on the lethal and sublethal effects of aluminum on
freshwater species are presented in Table 6. Bringmann and Kuhn (1959a,b)
found that Scenedesmus quadricauda was more resistant to aluminum in river
water than C.hlorella pvrenoidosa. They did not find any toxic effects on
Paphnia magna during a 48-h exposure to 1,000,000 m/L. Toxicity might
have been reduced by naturally occurring ligands in the river water.
Birge and coworkers reported that 507. of the embryos and fry of the
narrow-mouthed toad, goldfish, largemouth bass, and rainbow trout were killed
or deformed by exposure to aluminum concentrations of 50, 150, 170, and
560 m/L, respectively (Table 6). Freeman and Everhart (1971) obtained an
LC50 of 513 m/L with rainbow trout fingerlings, but these and other
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investigators also obtained much higher LCSOs with embryos, fry, and
fingerlinjs of rainbow trout. Freeman (1973) studied the growth of rainbow
trout after exposure to aluminum for 4.7 to 45 days. Growth was reduced by
5,200 MgA wnen pH was 7.0. 8.0, or 9.0. Normal growth resumed within two
weeks in control water.
Unused Data
Many data on the effects of aluminum on freshwater organisms were not
used because the pH of the dilution water used in the tests was less than 6.5
(Anderson 1948; Baker and Schofield 1982; Brown 1981,1983; Brown et al. 1983;
Buckler et al., Manuscript; Clark and LaZerte 1985; Cleveland et al. 1986;
Cook and Haney 1985; Dickson 1983; Driscoll et al. 1980; Eddy and Talbot
1983; Gunn and Keller 1984; Gunn and Noakes 1986; Havas and Hutchinson
1982,1983; Hunn et al. 1987; Jones 1940; Ogilvie and Stechey 1983; Orr et al.
1986; Schindler and Turner 1982; Schofield and Trojnar 1980; Staurnes et al.
1984; Tease and Coler 1984; van Dan et al. 1981; Witters et al. 1984). Data
were also not used if the studies were conducted with species that are not
resident in North America.
Burrows (1977), Chapman et al. (1968), Doudoroff and Katz (1953), Howells
et al. (1983). Kaiser (1980), McKee and Wolf (1963), Odonnell et al. (1984),
Phillips and Russo (1978), and Thompson et al. (1972) compiled data from
other sources. Test results (e.g.. Helliwell et al. 1983) were not used when
it was likely that they would have been substantially different if they had
been reported in terms of acid-soluble aluminum. Data were not used when
aluminum was a component of an effluent or a mixture (Buckler et al..
Manuscript; Guthrie et al. 1977; Hall et al. 1985; Hamilton-Taylor et al.
1984; Havts and Hutchinson 1982; Jay and Muncy 1979; Markarian et al. 1980).
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Becker and Keller (1983), Marquis (1982), and Stearns et al. (1978) were
not used because the results were not adequately presented or could not be
interpreted. Data were not used when only enzymes were exposed (e.g.,
Christensen 1971/72; Christensen and Tucker 1976). Tests conducted by
McCauley et al. (1986) at higher pHs were not used because the organisms were
not acclimated to the dilution water before the beginning of the test.
Control mortality was too high in many tests reported by Buckler et al.
(Manuscript).
Reports of the concentrations of aluminum in wild aquatic organisms
(e.g., Ecological Analysts, Inc. 1984; Elwood et al. 1976; Wren et al. 1983)
were not used when the number of measurements of the concentration of
aluminum in water was too small. Reports of other field studies were not
used when they either lacked adequate measurements of aluminum concentrations
in the water or reported no specific adverse effects (Berg and Burns 1985;
Brumbaugh and Kane 1985; Buergel and Soltero 1983; Gibbons et al. 1984; Knapp
and Soltero 1983; Sonnichsen 1978; van Coillie and Rousseau 1974; Zarini et
al. 1983).
Summary
Acute tests have been conducted on aluminum at PH between 6.5 and 9.0
with freshwater species in fourteen genera. In many tests, less than 50% of
the organisms were affected at the highest concentration tested. Both
ceriodaphnids and brook trout were affected at concentrations below
4,000 MC/L, whereas some other fish and invertebrate species were not
affected by 45,000 Mg/L. Some researchers found that the acute toxicity
of aluminum increased with pH, whereas others found the opposite to be true.
Three studies have been conducted on the chronic toiicity of aluminum to
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aquatic animals. The chronic values for Daphni a magna. Ceri odaphnia dubia.
and the fathead minnow were 742.2, 1,908, and 3,288 jug/L, respectively.
The diatom, Cvclote11 a meneghi ni ana, and the green alga, Se1enastmm
capri cornutum. were affected by concentrations of aluminum in the range of
400 to 900 ng/L. Bioconcentration factors from 50 to 231 were obtained in
tests with young brook trout. At a pH of 6.5 to 6.6, 169 ng/L caused a
24% reduction in the growth of young brook trout, and 174 ng/L killed 58%
of the exposed striped bass.
National Criteria
The procedures described in the "Guidelines for Deriving Numerical
National Water Quality Criteria for the Protection of Aquatic Organisms and
Their Uses" indicate that, except possibly where a locally important species
is very sensitive, freshwater aquatic organisms and their uses should not be
affected unacceptably, when the pH is between 6.5 and 9.0, if the four-day
average concentration of aluminum does not exceed 87 p.g/L more than once
every three years on the average and if the one-hour average concentration
does not exceed 750 ng/L more than once every three years on the average.
Implementati on
Because of the variety of forms of aluminum in ambient water and the lack
of definitive information about their relative toxicities to freshwater
species, no available analytical measurement is known to be ideal for
expressing aquatic life criteria for aluminum. Previous aquatic life
criteria for metals and metalloids (U.S. EPA 1980) were expressed in terms of
the total recoverable measurement (U.S. EPA 1983a), but newer criteria for
metals and metalloids have been expressed in terms of the acid-soluble
measurement (U.S. EPA 1985b). Acid-soluble aluminum (operationally defined
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as the aluminum that passes through a 0.45 ,um membrane filter after the
sample has been acidified to a pH between 1.5 and 2.0 with nitric acid) is
probably the best measurement at the present for the following reasons:
1. This measurement is compatible with nearly all available data concerning
toxicity of aluminum to, and bioaccumulation of aluminum by, aquatic
organisms. It is expected that the results of tests used in the
derivation of the criteria would not have changed substantially if thev
had been reported in terms of acid-soluble aluminum.
2. On samples of ambient water, measurement of acid-soluble aluminum will
probably measure all forms of aluminum that are toxic to aquatic life or
can be readily converted to toxic forms under natural conditions. In
addition, this measurement probably will not measure several forms, such
as aluminum that is occluded in minerals, clays, and sand or is strongly
B J
sorbed to particulate matter, that are not toxic and are not likely to
become toxic under natural conditions. Although this measurement (and
many others) will measure soluble complexed forms of aluminum, such as
the EDTA complex of aluminum, that probably have low toxicities to
aquatic life, concentrations of these forms probably are negligible in
most ambient water.
3. Although water quality criteria apply to ambient water, the measurement
used to express criteria is likely to be used to measure aluminum in
aqueous effluents. Measurement of acid-soluble aluminum is expected to
be applicable to effluents because it will measure precipitates, such as
carbonate and hydroxide precipitates of aluminum, that might exist in an
effluent and dissolve when the effluent is diluted with receiving water.
If desired, dilution of effluent with receiving water before measurement
of acid-soluble aluminum might be used to determine whether the receiving
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water can decrease the concentration of acid-soluble aluminum because of
sorption.
4. The acid-soluble measurement is expected to be useful for most metals and
metalloids, thus minimizing the number of samples and procedures that are
necessary. .
5. The acid-soluble measurement does not require filtration of the sample at
the time of collection, as does the dissolved measurement.
6. The only treatment required at the time of collection is preservation by
acidification to a PH between 1.5 and 2.0, similar to that required for
the total recoverable measurement.
7. Durations of 10 minutes to 24 hours between acidification and filtration
of most samples of ambient water probably will not affect the result
substantially.
8. Ambient waters have much higher buffer intensities at a pH between 1.5
and 2.0 than they do at a pH between 4 and 9 (Stumm and Morgan 1981).
«
9. Differences in pH within the range of 1.5 to 2.0 probably will not affect
the result substantially.
10. The acid-soluble measurement does not require a digestion step, as does
the total recoverable measurement.
11. After acidification and filtration of the sample to isolate the
acid-soluble aluminum, the analysis can be performed using either atomic
absorption spectrophotometric or ICP-atomic emission spectrometric
analysis (U.S. EPA 1983a), as with the total recoverable measurement.
Thus, expressing aquatic life criteria for aluminum in terms of the
acid-soluble measurement has both toxicological and practical advantages.
The U.S. EPA is considering development and approval of a method for a
measurement such as acid-soluble.
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The 0.45 urn membrane filter is the usual basis for an operational
definition of "dissolved," at least in part because filters with smaller
holes often clog rapidly when natural water samples are filtered. Some
particulate and colloidal material, however, might pass through a 0.45 Mm
filter. The intent of the acid-soluble measurement is to measure the
concentrations of metals and metalloids that are in true solution in a sample
that has been appropriately acidified. Therefore, material that does not
pass through a filter with smaller holes, such as a 0.1 Mm membrane
filter, should not be considered acid-soluble even if it passes through a
0.45 Mm membrane filter. Optional filtration of appropriately acidified
water samples through 0.1 Mm membrane filters should be considered
whenever the concentration of aluminum that passes through a 0.45 Mm
membrane filter in an acidified water sample exceeds a limit specified in
terms of acid-soluble aluminum.
Metals and metalloids might be measured using the total recoverable
method (U.S. EPA 1983.). This would have two major impacts because this
method includes a digestion procedure. First, certain species of some metals
and metalloids cannot be measured because the total recoverable method cannot
distinguish between individual oxidation states. Second, in some cases these
criteria would be overly protective when based on the total recoverable
method because the digestion procedure will probably dissolve some aluminum
that is not toxic and cannot be converted to a toxic form under natural
conditions. This could be a major problem in ambient waters that contain
suspended clay. Because no measurement is known to be ideal for expressing
aquatic life criteria for aluminum or for measuring aluminum in ambient water
or aqueous effluents, measurement of both acid-soluble aluminum and total
recoverable aluminum in ambient water or effluent or both might be useful.
For example, there might be cause for concern when total recoverable aluminum
13
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is much above an applicable limit, even though acid-soluble aluminum is below
the limit.
In addition, metals and metalloids might be measured using the dissolved
method, but this would also have several impacts. First, in many toxicity
tests on aluminum the test organisms were exposed to both dissolved and
undissolved aluminum. If only the dissolved aluminum had been measured, the
acute and chronic values would be lower than if acid-soluble or total
recoverable aluminum had been measured. Therefore, water quality criteria
expressed as dissolved aluminum would be lower than criteria expressed as
acid-soluble or total recoverable aluminum. Second, not enough data are
available concerning the toxicity of dissolved aluminum to allow derivation
of a criterion based on dissolved aluminum. Third, whatever analytical
method is specified for measuring aluminum in ambient surface water will
probably also be used to monitor effluents. If effluents are monitored by
measuring only the dissolved metals and metalloids, carbonate and hydroxide
precipitates of metals would not be measured. Such precipitates might
dissolve, due to dilution or change in pH or both, when the effluent is mixed
with receiving water. Fourth, measurement of dissolved aluminum requires
filtration of the sample at the time of collection. For these reasons, it is
recommended that aquatic life criteria for aluminum not be expressed as
dissolved aluminum.
As discussed in the Water Quality Standards Regulation (U.S. EPA 1983b)
and the Foreword to this document, a water quality criterion for aquatic life
has regulatory impact only after it has been adopted in a State water quality
standard. Such a standard specifies a criterion for a pollutant that is
consistent with a particular designated use. With the concurrence of the
U.S. EPA, States designate one or more uses for each body of water or segment
thereof and adopt criteria that are consistent with the use(s) (U.S. EPA
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1983c,1987). In each standard a State may adopt the national criterion, if
one exists, or, if adequately justified, a site-specific criterion. (If the
site is an entire State, the site-specific criterion is also a State-specific
criterion.)
Site-specific criteria may include not only site-specific criterion
concentrations (U.S. EPA 1983c), but also site-specific, and possibly
pollutant-specific, durations of averaging periods and frequencies of allowed
excursions (U.S. EPA 1985c). The averaging periods of "one hour" and "four
days" were selected by the U.S. EPA on the basis )f data concerning how
rapidly some aquatic species react to increases in the concentrations of some
pollutants, and "three years" is the Agency's best scientific judgment of the
average amount of time aquatic ecosystems should be provided between
excursions (Stephan et al . 1985; U.S. EPA 1985c). However, various species
and ecosystems react and recover at greatly differing rates. Therefore, if
adequate justification is provided, site-specific and/or pollutant-specific
concentrations, durations, and frequencies may be higher or lower than those
given in national water quality criteria for aquatic life.
Use of criteria, which have been adopted in State water quality
standards, for developing water quality-based per.nit limits and for designing
waste treatment facilities requires selection of an appropriate wasteload
allocation model. Although dynamic models are preferred for the application
of these criteria (U.S. EPA 1985c), limited data or other considerations
might require the use of a steady-state model (U.S. EPA 1986). Guidance on
mixing zones and the design of monitoring programs is also available (U.S.
EPA 1985c,1987).
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Table I. Acute Toxicity of aluminum to Aquatic Animals
Species Method*
Plonorion (odult). S. U
Ouqesi o t igr i no
Snail (adult). S. U
Physo sp
Snail (adult). S. M
Physo sp.
Snail (adult). S. U
Physo sp.
Snail (adult). S, M
Physo sp.
Cladoceran (23.000C >23.000
7 46 55.500d
6 59 >2i.400
7 55 30.600
8 17 >24.700 30.600
74 1.900 1.900
7 68 3.690 3,690
6 5- 3,900e
7 5
7 61 >25.300
7.05 38,200 38,200
7 53 22,000 22.000
Reference
Brooke et al. 1985
Call 1984
Call 1984
Coll 1984
Call 1984
UcCauley el al 1986
Call 1984
Biesinger and
Christensen 1972
Brooke et al 1985
K imloI I, Uanuscripi
Call 1984
Commorus pseudolimnaeus
chloride
-------
Table I. (continued)
StoneMy (nymph). S, M
Acroneuria sp.
Midge (lorvo), S. U
Tanytorsus dissimi 1 is
Chinook salmon $, u
(juveni le) ,
Oncorhynchus tsho»ytscha
Roinbb* trout S, U
(juveni le) ,
Salmo qoi rdneri
ftainboi trout S, y
(juveni le) ,
So Imo qoi rdneri
Rainboi trout S. U
(juveni le) ,
Salmo qoi rdneri
ftainbo* trout S, U
(juveni le) .
Salmo qoi rdneri
Brook trout F, y
(juveni le) ,
Solvelinus fontinalis
Fathead minnoi S, U
(adult),
Pimephol es prorael as
««'<••« IC50 Species Uea.
( («g/L «s or CC50 Acute Value
«**'ClL CaCOli_ Efi (22.600 >22,600 Call 1984
chloride
"*'""* 7 "- >79.900 >79.900 Lamb and Bailey 1981
sulfate e 85
S*><"U" 28 ° 7 ° >40,000 >40.000 Peterson et al 1974
aluminote
Aluminum 47 4 7 46 8.60011 - Call 1984
chloride
Aluminum 47.4 6 59 7,400 - Call 1984
chloride
Aluminum 47.4 7 31 14,600 - Call 1984
chloride
Aluminum 47 4 817 >24.700e 10.390 Coll 1984
chloride
*'uinint"" - 65 3,600 3,600 Decker ond Menende;
sulFate 1 974
Aluminum - 76 >I8,9UU - Boyd 1979
sul fate
-------
Table I. (continued)
oo
Species
Fathead minnon
( j uveni le) .
Pimephol es promelas
Fathead minno*
(juveni 1 e) .
Pimephales promelas
Fathead ainnoi
(juveni le) .
Pimepholes promelos
Channel catfish
(juveni 1 e) ,
Idol urus punc totus
Green sunfish
(juveni le) ,
Lepomi s cvonel 1 us
Yel lo* perch
(juveni le) .
Perca flavescens
Hardness LC50 Species Mean
(•g/L es or EC 50 Acute Value
Method* Chemical CuCO.) pH (/ia/L)b (na/1) Reference
S. M Aluminum 47.4 7.61 >48.200 - Call 1984
chloride
S. U Aluminum 47.4 8 OS > 49, 800 - Call 1984
chloride
F. M Aluminum 220f 7 34 35.000 35.000 Kimball. Manuscript
sul fate
S. U Aluminum 47.4 7 54 > 47. 900 >47.900 Call 1984
chlori de
S. U Aluminum 47.4 7 55 > 50, 000 > 50, 000 Call 1984
chloride
S, U Aluminum 47.4 7.55 > 49. 800 >49,800 Call 1984
chloride
S = static; R = renewal; F - fIo«-lhrough, U = measured; U = unmeasured.
Concentration of aluminum, not the chemical
48-hr test
Aluminum chloride was added to Lake Superior »o»er. the pH «as adjusted, and the solution «as aerated for 18 days prior lo addition
of test organisms, not used in calculations
Nat used in calculations
From Smi Hi et al (I97G)
-------
Table 2. Chronic Toxicity of Aluminum to Aquatic Aaieials
Hardness
Liaits
Chroeic Value
Species Test"
Cladoceran, LC
Ceriodophni a dubio
Cladoceran, LC
Oaphnio maqno
fotheod minnoi, CIS
Pimepholes prgmelos
Chemical CaCO,)
FRESHt
Aluminum 50
chlorida
Aluminum 22UC
sulfate
Aluminum 220°
sulfate
Eft
HATCH SPECIES
715
8 30
7 24-
8 15
1M/1\" (wd/ll
1.400- 1.908
2.600
540- 742 2
1 .020
2.300- 3,288
4.700
Reference
UcCauley et al 1986
Kimbal 1 , Uanuscr ipt
Kimball. Manuscript
LC = life-cycle or partial life-cycle; ELS = early life-stage
Measured concentrations of aluminum
from Smith et a) (1976).
-------
Table 2. (co««i»ued)
RaHo
Cladoceran,
Cladoceran.
Paohnio, mat
fathead •in»o«.
>i«ephoies o_roi»»ta£
Hardness
_CaCOjl_
50
220
220
Acut e Val ne
TIC \ 900 '
713"
7 4
742 2
7 05- iBl
8 30
7 24- J5.°UO *'
8 15
e
Ratio
0 9956
51 47
10 64
-------
Table 3. Ranked Genus Mean Acute Values lilh Species Uean Acute-Chronic Ratios
Genus Uean Species Uean Species Uean
Acute Value Acute Value Acute-Chronic
_ Species (null] Roti oc
14 >79,900 Midge, >79,900
Tonytorsus di ssimiI is
13 >50,QOO Green sunfish, >50,000
Lepomis cyonelI us
12 >49.800 Yello* perch, >49,800
Perco fIovescens
II >47.900 Channel catfish, >47.900
Ictolurus punctat us
10 >40,000 Chinook salmon. >40.00U
N) Oncorhynchus tshatry tscho
*-•
9 38.200 Cladoceran, 38.200 51 47
Oophnia moqno
8 35.000 Fatheod minnow. 35.000 10 64
Pimepholes promelas
7 30,600 Snail. 30.600
Physo sp.
6 >23,000 Planarian. >23,000
Dugesig t i qri no
5 >22,600 Stonefly, >22,600
Acroneur i a sp
4 22.000 Amphipod, 22.000
Commorus pseudolimnaeus
3 10,390 Rainbow trout, 10.391)
Sal mo go i rdner i
-------
Table 3. (continued)
N>
Genus
Acute Value
»o«k'
2 3.600
I 2.648
Brook trout ,
SolvelInus font i nolis
Cladoceran.
Ceriodophni o dubia
Cladoceran,
Cer i odophnia sp
Species Mean
Acute Value
3.60U
,9UO
3,690
Species Uean
Acute-Chronic
Ratio1
0 9958
Ranked fro* Most resistant to Most sensitive based on Genus Mean Acute Value
Inclusion of "greater than" values does not necessarily imply a true ranking, but does
allo* use of all genera for •hich data are available so that the Final Acute Value is
not unnecessarily loiered.
b From Table I
0 from Table 2
fresh »oter (pH betneen 6 5 and 9 Q|
Final Acute Value = 1.496 /jg/L
Criterion Maximum Concentration = (1.496 /jg/L) / 2 = 748 0
Final Acute-Chronic Ratio = 2 (see text)
Final Chronic Value - (1,496/jg/L) / 2 = 748 0//g/L
Final Chronic Value = 87 ftq/i (lowered to protect brook trout and striped bass, see text]
-------
u>
Table 4. Toxicity al Al«ainum to Aquatic Plants
Hardness
Spec i es
Diatom.
C y c 1 o t e 1 1 a meneqhi ni ana
Green alga,
Selenastrum copricornut urn
Green alga,
Selenastrum copr i cornut urn
Green alga,
Sel enastrum copri cornut urn
Eurasian latermi 1 f oi 1 .
Mvriophyl 1 urn spicotum
Ouck»eed.
lemno minor
Duckveed,
Lemno minor
Chemical pH
Aluminum 7 9
chloride
Sodium 7 0
aluminate
Aluminum 7 6
chloride
Aluminum 8.2
chloride
-
Aluminum 7 6
chloride
Aluminum 8 2
chloride
(mg/L es Duration
CaCOj]_ (days) Effect
FRESHWATER SPECIES
8 Inhibited gro«th
olgistat ic
algicidal
15 -14 Reduced cell
counts and
dry (eight
14.9 4 ECSO
( bi omass)
14 9 4 ECSO
(biomoss)
32 ECSO
(root Height)
14 9 4 Reduced frond
product ion
14.9 4 Reduced frond
product ion
Concentration
(uQ/L|a Reference
810 Rao and Subramanian
3.240 1982
6.480
990- Peterson et at 1974
1.320
570 Call 1984
460 Call 1984
2.500 Stanley 1974
>45.7QO Call 1984
>45.7QO Call 1984
Concentration of aluminum, not the chemical
-------
Table 5. lioaccuaylatio* of Aluaiiua by Aquatic Organisms
Hardness
Species
Brook trout (eyed embryo).
Sol vel i nus font i nol is
Brook trout (37 days).
Sal yel i nus font inol is
Concentration
Cheat col i* Voter (ua/ll*
Aluminum 242
sulfote
Aluminum 242
sulfote
(•9/1 as
_£SC°31_ £il Tissue
13 7 24 Whole
body
14 1 35 Whole
body
Durat io«
Post-hatch.
IS days
3Q days
IS days
30 days
BCF or
BAfb
147
SU
231
136
Reference
Cleveland et al 1986
Cleveland et al . 1986
Ueasured concentration of
Bioconcentration factors (BCfs) and biooccunulotion factors (BAfs) are based on measured concentrations of aluminum in Hater and
i n I issue
to
-------
Table 6. 01 her Data a* Effects of Aluminum on Aquatic Organises
K)
Species
Hardness
(mg/l as
Concent rot ion
Green alga,
Chlorel la vul qoris
Green alga.
Chlorel lo vulqor is
Green alga.
Scenedesmus quodr i coudo
Plonktonic communities
Protozoan,
Mi croreqmo heterostoreo
Protozoan ,
Chilomonas paramecium
Protozoan,
Peronemo tr ichoporum
Protozoan ,
Tetrohymeno pyr i I ormis
Protozoan ,
Euql end qroc i 1 i s
Cladoceran (mature),
Oophnio catoirbo
Aluminum
chloride
Aluminum
sul fat*
Aluminum
chlori de
Aluminum
sullate
Aluminum
chloride
Aluminum
chloride
Aluminum
chloride
Aluminum
chloride
Aluminum
chlori de
Aluminum 8 07
chloride
— r"- • «•! »•••»»•• i • I ei I IIJQ/I-I
fBEStUfATER SPECIES
<7 0 3-4 mo Inhibited 4, DUO
grout h
30 days Reduced maximum < 161, DUO
groit h
7 5- 96 hr Incipient 1,500-
^ 8 inhibi I ion 2,000
(river voter)
61- 1 br Decreased pbos- 50
6 9 phote uptake and
photosynthesis
7 5- 28 br Incipient 12,000
78 inhi bi t ion
(river later)
55- 3 hr Some 1 10
7 4 survi val
55- 3 hr Some 62,600
6 5 survival
5 5~> 3 hr Some 1 10
6 5 surv i val
60- 3 hr Some 1 1 1 , 800
7 0 survival
65 72 hr Reduced 1 ,020
surv i val
Hef erence
De Jong 1965
Becker and Keller 1971
Bringmonn and Kuhn
I959a,b
Nelewajko and Paul
1985
Sringmann and Kuhn
I959b
Ruthven and Cairns
1973
Rulhven and Cairns
I97J
Rut hven and Cu i rnv
I97J
Rut hven and Cu i r iii
1971
Huvo:> and I i k e/i%
-------
Table 6. (continued)
Species
Clodoceran,
Oophni o moqno
Cl odoceran.
Oophni o moono
Cl odoceran ,
Oophni o mogna
Cladoceran ,
Dophni o moono
ro
cr* Cladoceran,
Dophni o moqno
Cladoceran,
Oophni o moqng
Cladoceran,
Dophni o moqno
Cladoceron,
Dophni g moqno
Cladoceron,
Oophni o moqng
Cl adoceran,
Daphni g moqno
Cl odoceran ,
Pophn i o nioqng
Hardness
(•9/1 as
Chemical CaCOJ
Aluminum
swlfate
Ammonium
aluminum
sulfate
Potassium
aluminum
sulfate
Aluminum
chloride
Aluminum 45 3
chloride
Aluminum 45 3
chloride
Sodium 27 0
al umi note
Aluminum 8 26
chloride
Aluminum
chloride
Aluminum 8 26
chloride
Al umi num 33 35
chlor i de
Cokcentrat ion
pH Duration Effect (fia./L)°
16 hr Incipient 21 ,450
immobi 1 i zat i on
16 hr Incipient 21 .620
immobi 1 i zot i on
16 hr Incipient 21.530
immobi 1 i zat i on
75 48 hr Non-toxic 1.000. 000
(river >ater)
6 5- 21 days CCI6 (reduced 320
7 5 reproduction)
6 5- 21 days LC50 1.400
7 5
70 96 hr Mortality > 40, 000
65 48 hr Mortality 320
6.5 48 hr Loss of 1.020
sodi urn
65 24 hr BCf = 18.000 20
BCf = 9,600 320
BCf = II ,000 1 ,020
65 24 hr BCf = 18,000 20
• BCf -- 14.700 1 ,020
Reference
Anderson 1944
Anderson 1944
Anderson 1944
Bringmann and Kuhn
I959o
B i es i nger and
Christensen 1972
Biesinger and
Christensen 1972
Peterson et al 1974
Hovas 1985, Hauas and
Likens I985o
Hovos and Likens
i Sb'ju
Havab 1985
Hovo, ,985
-------
Table 6. (continued)
Species
Clodoceron.
Dophni a moqno
Crayfish.
Orconectes viri 1 is
Aquatic beetle (adult),
Tropistermus loterolis
nimbotus
Midge (larva),
Tgnytorsus dissimi 1 is
Roiaboe trout
(f ingerling) ,
Sqlmo qoirdneri
Rainboi trout
(embryo) ,
Sol no qqi rdneri
Rainbo* trout
(embryo, larva),
So Imp qoi rdneri
Rainboi trout
( juveni le) ,
So Imp qoirdneri
Rainbow trout
(embryo, larva) ,
Chemical
Aluminum
sulfate
Alumi a urn
chloride
Aluminum
chloride
Alumi num
sul fate
Al umi num
chloride
Al umi num
chlor i de
Alumi num
chloride
Aluminum
sul fate
A 1 umi num
sul fate
Hardness
(-9/1 as
c.co3i_
220b
II 0
-
17.43
46 8
28 3
28 3
56 6
56 6
-
104
(92-110)
25
14 3
pj
7 05
7 0
7 0
6 63
8.02
8 48
8 99
6.64
6 80
70-
9 0
74
70
8 0
8 5
9 0
6 5
7 2
Durat io»
48 hr
2 hr
14 days
55 days
32 days
7 5 days
3 days
44 days
39 days
Pert i 1 i zo-
t ion to
hatch
28 days
10 days
96 hr
42 hr
42 hr
8 days
[ffect
IC5U
((•*)
Calcium uptake
una I fee ted
Changed the
fat body
37Z dead
SOX dead
SOX dead
SOZ dead
SOZ dead
SOZ dead
No reduced
fert i lity
EC50 (death
and deformity)
OZ dead
40Z dead
IQUZ dead
IUUZ dead
No effect
No effect
Concentre! ion
iwn°
38.200
20U
200
832
5.230
S.I40
5.200
513
5,140
5.200
560
200.000
50,000
50,000
50,000
1 ,000
1 , 000
Reference
Kimbal 1 , Manuscript
Ual ley and Chang 1985
Wooldridge and Wooldridge
1969
Lamb and Bai ley 1981
Freeman and [verhart
19/1
[verhart and freeman
1973
Birge 1978, Birge et al
1978. I960, 1981
Hunter et al (980
Holtze !9Bi
SoImo qoirdner i
-------
Table 6. (continued)
Species
Roinboi trout
(eyed embryo),
So Imo goif dneri
Roinbo* trout
(juveni le) ,
Sol mo qoi rdneri
Brook trout
(eyed embryo) ,
Solvelinus fontinolis
Brook trout (37 days) .
Solvelinus fontinalis
00
Brook trout
(eyed embryo).
Sol vel inus font inol is
Brook trout (larva),
Solvelinus fontinalis
Brook trout
(embryo, larva),
Solvelinus fontinolis
Goldfish (60-90 mm),
Corassius ourot us
Coldf ish (juveni le) ,
Corassius ouratus
Hardness
(-9/L .s
Chemicel CdCOj)
Aluminum 14 3
sulfate
Aluminum
sulfate
Aluminum 13
sulfate
Aluminum 14
sulfate
Aluminum
-------
Tokle 6. (continued)
Species
Goldfish
(embryo, lorvo),
Corossi us ourotus
Common carp (juvenile).
Cyprinus carpi o
fathead minnow (adult) ,
Pimepholes nroroelos
fathead minnow
K> (juveni le) .
Pimephales promelas
Lorgemouth bass
(juveni le) .
Uicropterus solmoides
Uummichog (adult).
f undulus heterocl i tus
Uosqui tof ish
(adult female).
Gombusio a f f j n i s
Threespine stickleback
(adult).
Cast erosteus gcul eat us
Striped bass (159 days),
Uorone saxat i 1 is
Striped bass (195 days),
Uorone saxat ills
Hardness
l-9/l «
Chemical _CoCO,|_
Aluminum 195
chloride
Aluminum
chloride
Aluminum
chloride
Aluminum 220b
sulfate
Aluminum 64-80
sulfate
Aluminum
sul fate
Aluminum
chloride
Aluminum
ni trate
Aluminum
sul fate
Aluminum
sulfate
fjt Pure t ion Effect
74 7 days CC50 (death
and deformity)
65 48 hr JQZ dead
66 ioz dead
5QZ reduction
of acetylchol-
i nesterase
act i vi ty
73 8 days LC50
(fed)
66- 7 days 01 dead
74
36 hr IOOZ dead
120 hr IOOZ dead
43- 4 days LC50 (high
7 7 turbidity)
>7 0 10 days No toxici ty
65 7 days OZ dead
72 OZ dead
65 7 days OZ dead
72 OZ dead
Concentration
fua/Lt Reference
150 Birge 1978
4.000 Muromoto 1981
4,000
18,000 Olson and Christensen
1980
22,400 Kimboll. Manuscript
50,000 Sonborn 1945
2,210° Thomas 1915
I.I 00°
26.900 Wall en et al 1957
18.500
70 Jones 1939
390 Buckler et al . Manuscript
391)
3911 Buckler et al , Manuscript
3911
-------
Table 6. (continued)
Species
Striped bass (160 days),
Uorone saxat ills
Lorgeaouth bass
(embryo, 1 arva) .
Uicr opterus solmoides
Narro*-Moutbed load
( embryo. 1 arva) ,
Cost rophryne corol i nens is
Marbled salamander
(embryo, larva),
Ambystoma opocum
Hardness
("9/1 «
Chemicel CeCOjl
Aluminum
sulfole
Aluminum 93-105
chloride
AlumJAum 195
chloride
Aluminum 93-105
chloride
pjt Ourot ion
65 7 days
6 5
72
7.2
72- 8 days
7 8
74 7 days
72- 8 days
78
Concentrat ioe
Effect (uq/lV Reference
01 dead 87 2 Buckler et al , Manuscript
58Z dead 174 4
21 dead 174 4
IUOX dead 348.8
CC50 (death 170 Birge et al 1978
and deformity)
EC50 (death) 50 Birge 1978, Birge et al
and deformity) 1979
CC50 (death 2,280 Birge et al 1978
and deformity)
Concentration of aluminum, not the chemical
b From Smith et ol (1976)
c If the aluminum sulfate is assumed to be anhydrous.
-------
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