aquatic aluminum: chemistry, toxicology, and environmental prevalence∗
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Aquatic aluminum: Chemistry, toxicology, andenvironmental prevalenceW. Dickinson Burrows a & John D. Hem ba U.S. Army Medical Bioengineering Research and Development Laboratory , Fort Detrick,Frederick, Marylandb Water Resources Division , U.S. Geological Survey , Menlo Park, CaliforniaPublished online: 09 Jan 2009.
To cite this article: W. Dickinson Burrows & John D. Hem (1977) Aquatic aluminum: Chemistry, toxicology, and environmentalprevalence , C R C Critical Reviews in Environmental Control, 7:2, 167-216, DOI: 10.1080/10643387709381651
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AQUATIC ALUMINUM: CHEMISTRY,TOXICOLOGY, AND ENVIRONMENTAL PREVALENCE*
Author: W. Dickinson BurrowsU.S. Army Medical Bioengineering Research
and Development LaboratoryFort DetrickFrederick, Maryland
Referee: John D. HemWater Resources DivisionU.S. Geological SurveyMenlo Park, California
INTRODUCTION
Because aluminum (the most prevalent metal inthe earth's crust) is such a ubiquitous element, thequestion of its toxicity is more difficult to resolvethan that of the heavy metals such as arsenic.Thus, although the toxicity of soluble aluminumhas been demonstrated for a wide spectrum ofplants and animals, the overwhelming percentageof aluminum in the world is without measuredtoxic effect. Consequently, in compiling thisreport, every effort has been made to distinguishamong the forms of aluminum to which testorganisms have been subjected. This has notalways been possible because few investigators inthe past acknowledged the importance of docu-menting all test conditions. It has not beenunusual for an investigator to report that a level ofaluminum exceeded by many natural waterssupporting a healthy biological community is toxicto some organism. Further difficulties have re-
sulted from the failure to conduct tests andpresent data in a statistically meaningful manner.Aquatic toxicology is a recently developed field,and work published more than a few decades agois rarely quantitatively useful. Therefore, the fieldof aluminum toxicology has been reviewed notwith the intent of documenting existing aquaticenvironmental hazards, for there is no suchdocumentation, but of defining natural conditionsunder which aluminum might prove to be toxic.
The review of Sorenson et al.1 contains a recentdiscussion of environmental aluminum as it relatesto human health. The review includes discussionson mammalian toxicology, physiology, and phar-macology, and a compilation of aluminum levelsof food products and environmental samples.
TOXICITY TO AQUATIC ANIMALS
A meaningful evaluation of the toxicity ofaluminum (or any toxicant) to an aquatic animal
*This review is derived in the main from a technical report of the same title prepared by the author in 1974 for TheAluminum Association, 750 Third Avenue, New York, N.Y. 10017, under the direction of Associated Water and AirResources Engineers, Inc., Nashville, Tenn. The cooperation of both organizations is gratefully acknowledged, as is theassistance of Prof. Eric L. Morgan, Tennessee Technological University, in preparation of the original manuscript.
June 1977 167
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requires painstaking attention to experimentaldetail.2 A suitable animal must be selected andacclimated to laboratory conditions. Environ-mental conditions such as temperature, pH, andtoxicant level must be maintained and monitoredthroughout the test. Finally, precise records mustbe kept, and the significance of the data should bedetermined by means of the proper statisticalmethod. Most of the toxicity studies reported failto meet these standards, but they do permitevaluation of aluminum as a potential environ-mental hazard and illuminate areas in whichfurther investigation would be profitable.
In this section we have assumed that there arethree forms of aluminum in water: aluminateanion, molecular (suspended) aluminum hydrox-ide, and aluminum cation. We have furtherassumed that the toxicity of aluminum is afunction of concentration and pH alone and isindependent of the counterion, whether it issulfate, chloride, or nitrate. However, there aremany different cationic forms of aluminum, andthere is no reason to believe that they will be ofequal toxicity. This is further discussed in thesection entitled "The Chemistry of Aluminum inWater."
FishAcute
For fish, the acute toxicity level is generallyconsidered to be that concentration which resultsin death or obvious incapacitation within aspecified time interval. The static bioassay (inwhich the fish remain in the same vessel of waterthroughout the test) is simpler to conduct than thecontinuous-flow bioassay (in which the fish areexposed to constant water conditions) which isconsidered to be a better measure of intoxicationin natural waters, particularly with respect totoxicant level and dissolved oxygen. Most of thestudies reported in this section were conductedunder static conditions. Where tests extended overa few days, the common practice was to renew thetest water periodically. Acute toxicity data aresummarized in Table 1 for freshwater fishes and inTable 2 for marine fishes.
The first significant investigation of aluminumtoxicity was conducted in 1915 by Thomas,3 whodetermined the toxicity of aluminum sulfate tofresh water-acclimated killifish. As was frequentlythe case in the studies reported here, Thomas didnot clearly define whether his concentration data
were based on aluminum ion, on aluminumsulfate, or on the hydrated salt. However,assuming that the data were based on anhydrousaluminum sulfate, it appears that 1 to 2 mg Al perliter killed the fish in 3 to 5 days. Thomas notedthat the freshwater killifish were probably lesshardy than the marine killifish, but that "it wasimpossible to use these salts in sea water onaccount of the insoluble precipitates which were atonce formed." Goldfish, the choice of manyinvestigators4"10 are reported to survive indefi-nitely at a level of 1 mg/1 (pH 7.6), but arekilled in a day or less by aluminum concentrationsin excess of 20 mg/1. The most sensitive fish is thestickleback, which, according to Jones,11 survivesan average of 4 days at an aluminum nitrate levelequivalent to 0.13 mg Al per liter. Doudoroff andKatz23 have pointed out that the nitrate salt is notthe best choice because nitrate is usually at verylow concentrations in natural waters. Many otherspecies representing several families have also beenemployed in toxicity tests, with sensitivities fallingin the ranges presented in Tables 1 and 2. Most ofthese studies are deficient in at least one of thefollowing respects:
1. Toxicity was evaluated over too short aduration.
2. The pH of the test water was not con-trolled or, in some cases, not measured.
3. There was no attempt to characterize thewater used as to alkalinity, hardness, etc.
4. No attempt was made to standardize thetest animal in size or species. Only goldfish wereemployed by more than a few investigators.
The importance of pH control is clearly demon-strated in the work of Freeman and Everhart,14
who studied the effect of different aluminumspecies on rainbow trout fingerlings maintained incontinuous-flow aquariums. Test solutions con-taining 5.2 mg/1 of total aluminum were progres-sively more toxic to pH-acclimated fish at pH 7, 8,8.5, and 9 (Table 1). Because the proportion ofdissolved to suspended aluminum also increaseswith pH (Table 3), it appears that the acutetoxicity of aluminum hydroxide to rainbow troutis primarily due to the aluminate ion.
The soluble aluminum salts all hydrolize insolution, with a concomitant increase in acidityand decrease in pH if the buffering capacity of thewater is exceeded. The abrupt change in pH may
168 CRC Critical Reviews in Environmental Control
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Fish
KfflifishFundulus heteroclitus
GoldfishCarassius auratus
Carassius auratus +Carassius carassius
Water
HydrantHydrant
Tap; 64-80 ppmtotal hardness
Tap
HardHardHard
c3(—»~ J
UnspecifiedLargemouth bass
Micropterus salmoides
BluegillLepomis macrochirus
SticklebackGasterosteus aculeatus
—
Tap; 64-80 ppmtotal hardness
Tap; 60-84 ppmtotal hardness
TapTapTapTapTap
TABLE 1
Acute Toxicity of Aluminum to Freshwater Fishes
Agent
A12(SO4)3
A12(SO4)3
A12(SO4)3-18H2OA12(SO4)3-18H2OA1C13
A1K(SO4)2
A1K(SO4)2
A1K(SO4)2
A1K(SO4)2
A1C13
A12(SO4)3
A12(SO4)3
A12(SO4)3
A1F3
AlF,A1(NO3)3-9H2OA1(NO3)3-9H2OA1(NO3)3-9H2OA12(SO4)3
A12(SO4)3-18H2OA12(SO4)3-18H2O
A13(SO4)3-18H,O
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
Al concentration(mg/1)
2.2a
20a
>0.526.110.510.5
1.01350
370027001800450380
220014501100
56
20a
PH
5.6
Effect
Not lethal in 7 days
Ref.
—-
5.64.5
Unbuffered—
5.56.87.6-
4-64-64-6
5.6-65.6-6
ca. 4ca. 4ca. 4
-
5.64.5
Lethal in 36 hrLethal in 5 days
Survival >7 daysLethal in 15-24 hrLethalLethalLethal in 1-10 hrLethal to most in 12-96 hrNot lethal in 4 daysLethal in 2 hr
Lethal in 30 minLethal in 50 minNot lethal in 1 hrLethal in 30 minNot lethal in 1 hrLethal in 20 minLethal in 45 minNot lethal in 1 hr24 hr TLMb (?)
Not lethal in 7 daysLethal in 8-23 hr
33
44567778
99999999
10
44
0.070.10.130.20.3
76.66.05.55.2
Minimum lethal doseAverage survival, 7 daysAverage survival, 4 daysAverage survival, 2 daysAverage survival, 1 day
11-1311-1311-1311-1311-13
SO
a Author's dose data ambiguous.
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TABLE 1 (continued)Acute Toxicity of Aluminum to Freshwater Fishes
1a.
3"
3
1|3a.
Fish
Rainbow troutSalmo gairdneri
TroutUnspecified
California salmonMinnow
Unspecified
Mosquito fishGambusia afflnis
EelAnguilla faponica
Japanese killifishGoby
Water
TapTapTapTap
-—
Tap--
Tap; 42 ppmalkalinity
DistilledDistilled
-
TurbidTurbidTurbidTurbidTurbidTurbid
----
Agent
AlCl,AlCl,AlCl,AlCl,A13(SO4),A12(SO4),
A1(NH4)(SO4)3
A1K(SO4)3
A1K(SO4)3
A13(SO4),-18H,O
A 1 2 ( S O 4 ) , - 1 8 H J OA1,(SO4),-18H2OA1K(SO4)3
AlCl,AlCl,AlCl,A13(SO4),A1,(SO4),A13(SO4),
AlCl,AlCl,Al3*Al(OH),
Al concentration(mg/1)
5.25.25.25.251
605757
17
40a
8110.5
272729373869
0.272.74
70
PH
9.08.58.07.0-_
___
7.3
___
4.3-7.24.3-7.24.3-7.24.4-7.74.4-7.74.4-7.7
__
6.3-7.87-1
Effect
TL5 O ,b3daysTL 5 0 ,8daysTL, 0 , 32 daysTL5 0 , 39 daysSerious injury in 5 minNo effect
Float on side in 10 hr .Lethal in 15 hrLethal in 6 hr
No effect in 1 hr
Sick, but alive after 24 hrLethal in 2.5 hrLethal
96 hr TLM48 hr TLM24 hr TLM96 hr TLM48 hr TLM24 hr TLM
Not lethal in >50 hrLethal in 3.6 hrc
Not toxicNot toxic
Rel
141414141515
161616
17
18187
191919191919
20202121
b Concentration of aluminum resulting in death of 50% of test fish within stated time.c Average.
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TABLE 2
Acute Toxicity of Aluminum to Marine Fishes2
Fish
Speckled troutCynoscion nebulosus
RedfishSciaenops ocellatus
KillifishFundulus grandis
Fundulus similis
Sheepshead minnowCyprinodon variegatus
MulletMugil cephalus
(Agent, AICI3)
Al concentration(mg/1)
91836
91836
1827369
1836
91836
182736
PH
6.1-7.55.5-6.7
4.8
6.1-7.55.1-5.6
4.8
5.1-6.84.9-5.04.6-4.86.1-7.55.5-6.74.9-5.0
6.1-7.55.5-6.74.6-5.0
5.5-5.64.6-5.04.9-5.0
Effect
Not lethal in 14 daysLethal in 7 daysLethal in 30 min
Not lethal in 11 daysLethal in 0.5-2 hrLethal in 45 min
Not lethal in 11 daysLethal in 4-96 hrLethal in 4-24 hrNot lethal in 11 daysLethal in 8 daysLethal in 4-96 hr
Not lethal in 11 daysLethal in 9 daysLethal in 1 day
Lethal in 1 dayLethal in 1 dayLethal in 4 hi
aNo more than three fish used in any test.
Data from Pulley.21
TABLE 3
Distribution of Aluminum as a Function of pHa
Totalaluminum
added(ppm)
5.2
0.52
0.052
7.0
l%diss.99% susp.10% diss.90% susp.
100% diss.
8.0
10% diss.90% susp.
100% diss.
100% diss.
PH
8.5
32% diss.68% susp.
100% diss.
100% diss.
9.0
100% diss.
100% diss.
100% diss.
adiss., dissolved; susp., suspended.
Adapted from Freeman, R. A. and Everhart, W. H., Trans. Am. Fish. Soc, 100,644,1971. With permission.
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be responsible for the death of fish. Furthermore,the source of the water may be important indetermining the toxicity of aluminum, becausewater of high alkalinity and intermediate pH willconvert the aluminum salt to the insolublehydroxide. If the aluminum cation is more toxicto fish than undissolved aluminum hydroxide, as isthe case with mammals, the same weight ofaluminum salt in water should become more toxicas the pH is decreased from the isoelectric point.Freeman and Everhart14 did not extend theirstudies below pH 7; therefore, increasing toxicitywith decreasing pH remains to be verified. Ellis7
has pointed out that natural waters with pH levelsas low as 4.5 (as bogs) or as high as 9.5 (as somemineral springs) may support fish life.
The turbidity of the receiving water may be asimportant as the alkalinity in moderating alu-minum toxicity. As Schaut17 has pointed out, "inthe mixing chambers of the average rapid sandfilter plants, where higher doses of alum areused . . . , fish life may be observed at any time."17
Wallen et al.19 have examined the toxicity ofaluminum in turbid waters. Gambusia were chosenas the test fish, eliminating any comparison withother studies; the pH was not controlled; and somesurvival times varied widely with little change indose, indicating difficulty in maintaining uniformconditions. Nevertheless, it is apparent that alu-minum in turbid waters is significantly less toxicthan indicated in any of the other studies, as dosessmaller than 20 mg Al per liter had no observedeffect. The most reasonable interpretation of theseresults is that the aluminum absorbed on colloidalsoil particles is not toxic to fish. Because mostaluminum introduced into wastewaters is added inorder to reduce turbidity, and because mostreceiving waters are at least somewhat turbid, it islikely that very little free aluminum will exist inthe receiving waters for any length of time. Mostof the experiments described, including those ofFreeman and Everhart,14 were conducted in tapwater that had previously been treated with alumto remove turbidity.
Our knowledge of the effects of aluminumintoxication on marine fishes is derived from asingle study by Pulley.22 The data are based onobservation of a small number of individuals, butit appears that aluminum levels below 10 mg/1 arenot toxic in 11 days to a variety of fishes in seawater (Table 2). This indicates a significantlylower degree of aluminum toxicity than do the
studies with tap water. There may be many causes.The seawater used had high alkalinity and alumi-num chloride doses greater than 10 mg Al per literwere required in order to reduce the pH below 6(compare, e.g., with the data for sticklebacks inTable 1). Furthermore, the natural environment ofmarine fishes includes a level of dissolved solidsthat would be toxic to most freshwater fish, andsea water animals may be better acclimated topolyvalent salts. Pulley22 has noted that agedsolutions of aluminum chloride in sea water areless toxic than freshly prepared solutions. Possiblereasons for this are discussed in the sectionentitled "The Chemistry of Aluminum in Water."
The effect of temperature on aluminum intoxi-cation is undetermined. Investigators who reportedtest temperatures usually worked at a singletemperature in a range favorable to the fish.
ChronicFreeman24 and Freeman and Everhart14'25
have performed a partial chronic bioassay foraluminum using the growth rate of rainbow troutin continuous flow aquariums. Fingerlings 11 to26 weeks old were maintained for as long as 45days in waters containing 0.05, 0.52, and 5.2 mgAl per liter at various pH levels. The results aresummarized in Table 4.
At pH 8, 90% of 5.2 mg Al per liter issuspended and 10% dissolved, as shown in Table 3.Feeding activity diminished within 24 hr, and gillhyperplasia (a swollen, congested condition) wasevident within 5 days in many of the trout. Thephysical condition of all fish continued todeteriorate, with individuals suffering frominability to maintain equilibrium, general listless-ness, loss of fright reaction, loss of negativephototaxis, darkening in coloration, and eventualdeath. Almost none of the trout exposed for thefull 45 days survived, even after transfer touncontaminated water. When exposed only todissolved aluminum (0.52 mg/1) at the same pH,fish exhibited milder forms of the symptomsdescribed above, with slower development ofhyperplasia and loss of appetite. Mortality wasgreatly reduced, recovery was rapid and almostcomplete within 48 hr of transfer to uncontami-nated water, and normal weight gain resumed. Analuminum level of 0.05 mg/1 had no apparenteffects.
At pH 8.5, 32% of 5.2 mg/1 aluminum isdissolved and at pH 9, 100% is dissolved. The
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Exposure time (days)Weight change during
bioassay (%)Mortality during
bioassay (%)Recovery time (days)Weight gain duringrecovery relative tocontrol weight gain (%)
Mortality duringrecovery (%)
Chronic Aluminum
Control
45+182
2
290100
3
pH7
0.52
45-3
44
290164
5
5.2
45-26
58
290195
16
TABLE 4
Intoxication and Recovery
Control
45+192
0
16100
-
for Trout
Al concentration
pH8
0.52
45+76
8
16101
0
5.2
45-18
77
1—
83
PH
Control
9.25+50
0
161100
5
8.5
5.2
9.25-32
51
161159
3
pH9
Control
4.7+84
0
165100
2
5.2
4.70
67
165141
2
Adapted from Freeman14 and Everhart and Freeman.2 5
above severe symptoms appeared in fish exposedto these conditions, but they appeared morerapidly. In addition, fecal casts were evident.Exposure was terminated after 222 hr and 113 hrat the two pH conditions, respectively. On transferof surviving trout to clean water, recovery wasrapid in the first case and delayed, but apparentlycomplete, in the second.
At pH 7, 99% of 5.2 mg/1 aluminum wassuspended. Symptoms were similar to those at pH8, although they developed more slowly andmortality was slightly lower. Recovery in cleanwater was very slow. Fish exposed to 0.52 mg/1 ofaluminum at pH 7 (90% suspended) exhibitedmilder symptoms, but the mortality over 45 dayswas much higher than at pH 8 and recovery wasvery slow. The results of Freeman24 and Freemanand Everhart14'25 can be summarized as follows:
1. Aluminate ion is acutely toxic to trout atlevels of 0.5 mg/1 and greater. Recovery is rapid ontransfer to uncontaminated water.
2. Aluminate ion also causes chronic injury,viz., gill hyperplasia. Recovery on transfer toclean water is rapid, perhaps because fish with ex-tensive chronic damage will already have succumb-ed to acute effects.
3. Freshly precipitated aluminum hydroxidedoes not cause acute intoxication of fish in theusual sense, but it can cause chronic injury.The symptoms are similar to those induced by
aluminates, but they are much slower in develop-ing and recovery is very slow.
The ultimate cause of death in aluminum-intoxicated fish is probably anoxia (suffocation)brought about by damage to the gills. Skidmore26
has presented evidence that damage to the gillepithelium by soluble zinc decreases thepermeability of the gills to oxygen. This work isconfirmed by Burton et al.,27 who suggest thatpoisoning by other metals may also result in tissuehypoxia. The onset of hypoxia would explainmost of the symptoms observed in aluminumpoisoning. For example, the loss of negativephototaxis is in agreement with the work ofNegishi and Sugawara,2 8 who observed that light-induced responses in isolated carp retinas areabolished by a brief period of anoxia. It is notclear why the onset of symptoms and recoveryfrom these symptoms should be more rapid withaluminate ion than with aluminum hydroxide. Itmay be that the mechanisms of gill damage bydissolved and suspended aluminum are different,or that fish exposed to aluminate suffer systemicintoxication as well as gill damage.
Aluminum is not reported to be very toxic tofish eggs. Mathews29 has found that Af/80aluminum chloride (338 mg Al per liter) is theminimum level preventing the appearance of theembryo in a significant number of eggs fromFundulus heteroclitus. Everhart and Freeman,2 s
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working with the same aluminum doses and pHlevels described previously, did not find substantialevidence for toxicity to the roe of rainbow trout.A Japanese paper30 reports that aluminum(concentration unknown) is toxic to salmon eggs.
Concerning the toxicity of metallic aluminum,a single report3' states that aluminum containersare toxic to various freshwater fishes and rivercrabs (Astacus sp.) in waters low in calcium. Alleeet al.32 have presented evidence for growthinhibition by aluminum in goldfish. Fish raised inwater prepared using an aluminum-lined still grewsignificantly more slowly than fish raised indistilled water from a different source. However,in the absence of aluminum analyses for therespective waters, any conclusions are speculative.
Other Aquatic VertebratesPincussen33 has reported that Bufo tadpoles
are dead after 20 hr of exposure to watercontaining N/10 aluminum chloride (2700 mg Alper liter). All tadpoles maintained in the dark arestill alive after 1-hr exposure, while 67% of thoseintermittently exposed to light are dead. Thealuminum levels maintained in these experimentsare too high to provide useful informationconcerning aluminum in the environment.Subcutaneous injection of 13 mg Al per kilogrambody weight (as aluminum sulfate) into anunspecified frog was without observed conse-quences, suggesting that amphibians are notuncommonly sensitive to systemic aluminum.34
Aquatic InvertebratesToxicity data for aquatic invertebrates are
summarized in Table 5. The microcrustaceanDaphnia magna is a common choice for acutebioassay, and several aluminum toxicity studieshave been conducted using this animal.Anderson35'36 has found that 22 mg/1 ofaluminum will immobilize Daphnia maintained inLake Erie water in 20 hr, while Daphnia exposed to1.4 mg/1 aluminum are immobilized in 64 hr. Morerecently, Biesinger and Christensen3 7 have report-ed the same order of acute toxicity for Daphnia inwater from Lake Superior. In 3-week chronic tests,a 16% reproductive impairment was observed at alevel of 0.32 mg/1. At complete variance with thesereports is a paper which states that Daphnia inriver water are unaffected by 1000 mg/1 in 4days.3 8 Based on observation of a few animals, themarine shrimp Penaeus setiferus appears to be
more hardy than Daphnia, enduring 9 mg Al perliter for more than 21 days.22 Only one mollusk,the oyster, has been studied and found to survivefor 10 to 11 days at 36 mg/1, pH 4.6 to 4.8.22
Jones39 has studied the effect of metal ionintoxication on the planarian Polycelis nigra bythe same techniques he previously used forstickelbacks. The 48-hr toxicity threshold (themaximum metal concentration at which themortality is the same as that of the control) wasdetermined to be equivalent to 110 mg Al per literfor aluminum nitrate at pH 4.2. (P. nigra is able toendure hydrochloric acid solutions of pH 3.6without lethal effect). Environmental aluminumseems unlikely to be a problem for flatworms.
The only research on echinoderms concerns thetoxicity of metals to the eggs of the sea urchinArbacia punctulata. Waterman40 found thatexposure for 13.5 hr to 24 mg Al per liter largelyinhibited gastrulation of the embryo. This inhibi-tion was reversed by transfering the eggs touncontaminated sea water, but some abnormalitiesof arm and skeletal formation appeared in thedeveloping animals. Some signs of inhibition wereobserved after exposure for 13.5 hr at 10 mg/1,and all embryos were killed by contact for 2.5 hrwith 40 mg Al per liter.
TOXICITY TO MICROORGANISMS
ProtozoaAccording to Reznikoff,41 the mean survival
time for Amoeba proteus in Af/128,000 aluminumchloride (0.2 mg Al per liter) is 3 days, indicating arelatively high level of sensitivity. In solutionsstronger than 0.01 mg Al per liter, A. proteusundergoes a gross enlargement of the contractilevacuole. In weak solutions (<0.05 mg Al per liter)this enlargement is temporary, with completerecovery of the animal. These amoebae are highlysensitive to acidic conditions. Reznikoff41 did notdistinguish between lethal effects due to acidityand those due to the aluminum ion alone, and thequestion of the toxicity of suspended aluminumwas not considered. Bringmann and Kuhn42 havefound the 28-hr toxicity threshold of aluminumchloride for the free-living ciliate Microregmaheterostoma to be 12 mg Al per liter at pH 7.5 to7.8 and 27°C. (The corresponding level for thegreen alga, Scenedesmus quadricauda, was re-ported to be one seventh as great under similarconditions.)
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Animal
ArthropodsDaphnia magna
Penaeus setiferus(shrimp)
OysterOstrea virginica
PlanarianPolycelis nigra
Water
Lake Erie,centrifuged
Lake Superior
River HavelSea
Tap
TABLE 5
Acute Toxicity of Aluminum
Agent
A1,(SO4)3
A1(NH4)(SO4)2
A1K(SO4),AICI3AlCl,A1C1,AlCl,
AICI3
AlCl,AlCl,
AlCl,AICI3
AICI3AlCl,AICI3
A1(NO,)3
i to Invertebrates
Al concentration(mg/1)
22
2222
1.43.91.40.68
0.32
10009
1836
182736
no
PH
Unbuffered
UnbufferedUnbuffered
7.5-8.26.5-7.56.5-7.56.5-7.5
6.5-7.5
—6.1-7.5
5.5-6.84.7-4.8
5.5-6.84.6-5.04.6-4.8
4.2
Effect
Immobilization in 16 hr
Immobilization in 16 hrImmobilization in 16 hrImmobilization in 64 hr48-hr LC s o
a
3-wkLC5Oa
50% reproductive impairment in3 weeks
16% reproductive impairment in3 weeks
No effect in 4 daysNot lethal in 21 days
Lethal in 2 .5 ->21 daysLethal in 1.5-2 hr
Not lethal in 11 daysLethal in 9 - > 11 daysLethal in 10 -11 days
48-hr survival threshold
Ref
35
353536373737
37
3822
2222
222222
39
a Concentration of aluminum resulting in death of 50% of test animals within stated time.
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Sleigh's43 studies on the action of aluminumion on the trumpet-shaped protozoan Stentorpolymorphus have been directed primarily towardelucidation of stimulation of ciliary movement.Aluminum chloride at approximately 1 mg Al perliter causes a 15 to 20% increase in ciliaryfrequency, an effect believed to result from adecrease in viscous resistance of protoplasm. Thefrequency falls off rapidly at higher concen-trations, indicating a probable lower toxicity limitof about 2 mg Al per liter at pH 6.8.
BacteriaMost of the studies concerning toxicity of
aluminum to bacteria have been directed towardsoil species rather than aquatic species. Zwarun etal.44 have shown that survival of a Bacillus speciesis reduced by about 20% after incubation for 3 hrat pH 4.5 with 80 mg/1 of soluble aluminum.However, other data indicate that this organism ismore sensitive to pH than to aluminum concen-tration. Zwarun and Thomas45 have found thatPseudomonas stutzeri (a saprophytic heterotrophcapable of reducing NO3—N to elemental nitro-gen) is highly sensitive to soluble aluminum, withits survival reduced by more than 95% afterincubation for 3 hr with 1 mg Al per liter at pH4.5. P. stutzeri is also sensitive to pH, but,curiously, addition of aluminum-saturated bento-nite to the culture provides protection against theadverse effects of both low pH and moderateconcentrations of aluminum. Because bacteriatend to adsorb onto clay particles, the toxicity ofaluminum to Pseudomonas in natural waters maybe quite low. The nitrogen-fixing bacteriumAzotobacter chroococcum exhibits significant in-hibition at 2.7 mg/1 of soluble aluminum46 and iscompletely killed in 3 to 7 days by solublealuminum at a level of 24 mg/1 at pH 5.8 to 6.6.47
As with the higher plants, the toxicity of alumi-num appears to be greatly enhanced in acid soils.Of interest in this respect is a study by Ornstein48
which showed that aluminum at the level of 9 mg/1is toxic to Staphylococcus aureus at pH 6.6, butnot at pH 7.3 or 8.0. The effects of aluminum onvarious bacteria are summarized in Table 6.
Several studies have been conducted on theeffect on bacteria of exposure to sublethal dosesof aluminum. Aluminum at the 10 jig/1 level altersthe course of fermentation by Aerobacter aero-genes and stimulates the production of certain Bvitamins.516 Aluminum has the interesting prop-
erty of limiting the production of flagella inBacillus megaterium at high, but sub-bacteriostatic(<32 mg/1) levels.S7 Aluminum sulfate added atthe level of 2.8 mg Al per liter to buffered
•synthetic sewage reduces the measured biologicaloxygen demand (BOD) by 50%.58 As BOD testsare carried out without agitation, it is possible thatthe effect of aluminum hydroxide is to precipitatethe microorganisms, thereby isolating them fromthe food supply and not a specific toxic effect.
The mycoplasmas (primitive bacteria whichpossess a cell membrane, but lack a rigid cell wall)are subject to destructive osmotic lysis whentransferred from a hypotonic solution to deionizedwater. Razin59 has found that aluminum ionconcentrations from 0.008 to 100 mg/1 preventosmotic lysis and, hence, the death of Mycoplasmalaidlawii. The prevention of osmotic lysis is ageneral effect of polyvalent ions, not a specificeffect of aluminum. However, it does indicate thataluminum is not especially toxic to mycoplasmasat pH 7.
Evidence concerning the toxicity of metallicaluminum to bacteria and other microorganisms isconflicting.60"64 Although aluminum containersare reported to be bactericidal with respect to E.coli,60 bacterial colonies are known to form onaluminum surfaces in sea water62 and somenonfouling alloys have been reported to show amarked increase in biofouling on addition of smallpercentages of aluminum.64 Aerobically culturedAlcaligenes faecalis is reported to be inhibited by3% aluminum powder, some of which appears assoluble aluminum in the medium and incorporatedin the cells.63 The growth rates of Micrococcuscaseolyticus and Pseudomonas aeruginosa are ac-celerated, while those of Aerobacter aerogenes andBacillus cereus mycoides are unaffected. Becauseexposed aluminum surfaces are always oxidized, itis probable that the chemistry and, hence, theacidity of the organism attempting to colonize (orthe acidity of those organisms which have alreadycolonized successfully) will determine the avail-ability of soluble aluminum, the most toxicspecies.
There are bacteria (including Bacillus muci-laginosus and B. cartilaginosus) which are reportedto derive some essential elements by breakdown ofaluminosilicates.6 s~6 7 Potassium, phosphorus, and(in the case of the silica bacteria) silicon may beextracted, releasing alumina and excess silica andpotash.6 s
176 CRC Critical Reviews in Environmental Control
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Bacterium
Bacillus sp.
Pseudomonas stutzeri
Azotobacter chroococcumAzotobacter vinelandiiAzotobacter chroococcumStaphylococcus aureusAcetobacter melanogenumEscherichia coli
Sporogenic bacteriaProteus vulgarisMycobacterium smegmatisBacterium phosphorescens
indigenusAerobacter aerogenes
Bacillus megaterium
Sewage bacteriaMycoplasma laidlawiiE. coliFour Bacillus spp. andSarcina agilis
Bacillus mycoidesMicrococcus caseolyticusPseudomonas aeruginosaAerobacter aerogenesBacillus cereus var. mycoidesAlcaligenes faecalis
Substrate
Acetate buffer
Acetate buffer
Glucose agarGlucose agarGlucose agarPhosphate bufferSorbitolUnknown
UnknownPicklesUnknownUnknownUnknown
Glucose
Glucose
Synthetic sewageWaterWaterNutrient broth
Sea waterNutrientNutrientNutrientNutrientNutrient
TABLE 6
Effect of Aluminum on Bacteiia
Agent
A1C1,
A i d ,
AlCl,AlCl,A1C1,AICI3Al 3 t
A13+EDTA
Al3+
AlumsAl3+
Al3 t
Al3+
A1,(SO4)3
AlCl,
A1,(SO4),AlCl,Al metalAl metal
Al metalAl metalAl metalAl metalAl metalAl metal
Al concentration(mg/1)
80
1
2.72.7
249
500Unknown
100500
UnknownUnknownUnknown
0.01
32
2.8100
3%3%3%3%3%
PH
4.5
4.5
5.8-6.66.6-
6-8
——-——
5.6-6
7
Buffered7
—-—-—
Effect
20% reductionin survival
>95% reductionin survival
InhibitionInhibitionLethal doseLethal doseMinimum level for inhibition"Exceptional antibacterial
activity"No effect observedNo effectToxicity: Cu>Al>CaToxicity: Mg >Al>PbToxic at high concentration,
stimulates at low concentrationIncreases B vitamin andpantothenic acid synthesis
Maximum sub-bacteriostaticdose; incomplete flagella-tion
50% reduction in BODNot toxic in 30 minInhibitoryWeakly inhibitory
NoninhibitoryGrowth acceleratedGrowth acceleratedNoneNoneGrowth inhibited
Ref
44
45
464647484950
5152535455
56
57
58596061
626363636363
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FungiThe fungi exhibit a wide range of sensitivities to
aluminum intoxication. Levy68 has found thatsoluble aluminum at levels as high as 200 mg/1 hasno effect on the development of the mold Steri-gmatocystis nigra. Appearance of the conidia isretarded at 350 mg/1, and there is no formation ofmycelia at 500 mg/1. Acidity is claimed to enhancethe toxicity of soluble aluminum only below pH2.7. Similarly, growth of the decay mold As-pergillus niger is inhibited by soluble aluminumlevels above 400 mg/1,6 9 but is retarded at levelslower than 20 mg/1, indicating some trace nutri-tional requirements.70 Neurospora tetrasperma iscomparatively sensitive, and its spores fail togerminate in solutions containing 0.65 mg Al perliter at pH 4.5.71 However, germination is un-inhibited at pH 7. Altemaria tenuis suffers 50%inhibition of germination at 0.35 mg Al perliter.72 The fungal pathogens of cotton73 '74 andsunflower75 are intermediate in sensitivity tosoluble aluminum. The yeasts (Saccharomycescerevisiae) are reported to vary greatly in re-sistance to soluble aluminum.76 '77 Curiously, thedevelopment of the mold Oospora lactis, whengrown on a particular strain of yeast, is stimulatedby 5 X 10"• M aluminum.78 The effects ofaluminum on fungi are summarized in Table 7.
AlgaeA series of investigations79 has been conducted
based on an early observation that Spirogyra cellsbriefly exposed to aluminum nitrate solution donot undergo plasmolysis when transferred to sugarsolution. Various proposals have been advanced toexplain this phenomenon, but current research isconcentrating on the plasmalemma, a thin mem-brane which surrounds the protoplasm within therigid cell wall of plant cells. Bohm-Tuchy,79 whohas briefly reviewed this research through 1960,has studied the effect of subjecting various algalspecies to different concentrations of aluminumnitrate for different periods of time prior toplasmolysis.79 This work has been directed towardelucidation of a problem in cell physiology ratherthan estimation of aluminum toxicity; thus,Bohm-Tuchy79 has compiled a record of manydetailed observations on the changes in cell proto-plasm resulting from plasmolysis in glucose solu-tion following aluminum exposure. From thesedata, the minimum doses known to kill the algaewithin an established time are given in Table 8; the
lesser injuries reported by Bohm-Tuchy79 forweaker solutions would probably also result indeath of the cell. Hofler84 has suggested that algae(such as Spirogyra) which lack well-developed.plasmalemmas are penetrated by aluminum ion,resulting in solidification of the outer layer ofprotoplasm, which is then less subject to plas-molysis. The stout plasmalemmas of Zygnema, onespecies of peat bog Spirogyra, and some higherplant cells protect the protoplasm from metal ions.
Another significant toxicity study related tocell physiology was conducted by Foy andGerloff,8 ° who found that Chlorella pyrenoidosa(a green alga which has no measurable calciumrequirement) tolerated much higher aluminumconcentrations in solution than higher plants,which require considerable calcium. Toxicity datareported in Table 8 for C. pyrenoidosa, whichwere measured for an aluminum-tolerant straindeveloped by Foy and Gerloff,80 indicate that 50mg Al per liter results in only slight inhibition ofgrowth at pH 4.6. In a study of the effects of acidmine water constituents on the growth dynamicsof Chlorella vulgaris, Becker and Keller8 * foundthat an aluminum sulfate concentration of 2012mg/1 (317 mg Al per liter) inhibited growth byabout 50% after 4 weeks. However, the sameconcentration of calcium sulfate was equally inhi-bitory. For C. vulgaris, an optimum nutritive levelof 8.7 mg Al per liter is indicated.85 In contrast,Bringmann and Kuhn38 place the toxicity thres-hold for Scenedesmus quadricauda at only 1.5 to 2mg/1.
The only marine alga for which toxicity datawas found is the sea lettuce Ulva lactuca.*3 Thismacroscopic green alga is considered in this sectionfor reasons of taxonomic consistency. The firstindication of growth inhibition in Ulva sporelingsappears after 9 days at a concentration of 0.002mg Al per liter, although significant inhibition isnot apparent below 0.2 mg/1. The latter figurecorresponds to a high degree of sensitivity toaluminum, considering that the pH was maintainedat 8.2 throughout the experiment.
All the algae discussed in this section aremembers of the class Chlorophyceae, the greenalgae. As Desmidiaceae and Zygnemaceae aredivisions of the same order (Conjugates), it isperplexing that there are such extreme differencesin sensitivity to aluminum salts in their environ-ments. One can speculate that the Desmids, whichproliferate in oligotrophic waters, evolved under
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TABLE 7
Fungus
Sterigmatocystis nigra
Aspergillus nigerNeurospora tetrasperma
Alternaria tennisBotrytis FabaeFusarium vasinfectum
Phymatotrichum omnivorumVerticillium albo-atrum
Whetzelinia sclerotiorum
Saccharomyces cerevisiae
Substrate
Sucrose medium
Sucrose mediumNutrient mediumNutrient solution
Nutrient solution
Malt agarLiquid dextroseCotton oil
Sucrose mediumNutrient mediumNutrient mediumNutrient mediumNutrient mediumSugar culture
The Effect of Aluminum on Fungi
Agent
A1,(SO4)3
A1,(SO4),A12(SO4),A1,(SO4),
A1,(SO4),
A1,(SO4)3A1,(SO4)3
AI
A1,(SO4)3
Ala(SO4)3
A1,(SO4)3
A1,(SO4)3
A1,(SO4)3
Al , (S0 4 ) ,
AI concentration(mg/1)
350
500800
0.65
0.65
0.353.8
50
200ca. 4ca. 8ca. 8ca. 32540
PH
Unbuffered
UnbufferedUnbuffered
4.8
7.0
5.04.4-
6.84.54.54.03.7—
Effect
Inhibited growthof conidia
Complete inhibition75-80% growth inhibitionComplete inhibition
of germination<5% inhibition ofgermination
ED s oa
ED s oa
50% inhibition ofgermination
Complete inhibition30% growth inhibition95% growth inhibition12% growth inhibition78% growth inhibitionCulture killed
Ref
68
686971
71
727273
747575757576
a Dose causing 50% inhibition of spore germination.
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TABLE 8
Effect of Aluminum on Algae
Alga
Zygnemaceae
Spirogyra variansSpirogyra RMK
(peat bog)Mougeotia sp. IMougeotia sp. IllZygnema sp. IIZygnema sp. Ill
Oedogonium
Oedpgpmium sp.
Desmidiaceae
Closterium sp.Pleurotaertium sp.Tetmemoms granulatusEuastrum sp.Micrasterias rotataCosmarium con trac turnXanthidium sp.Staurastrum sp.Desmidium swartziiNetrium digitus
Medium
Fresh waterFresh water
Fresh waterFresh waterFresh waterFresh water
Agent
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO,)3
A1(NO3)3
A1(NO3)3
Freshwater A1(NO3)3
Al concentration(mg/1)
0.13527
2713.527
270
27-135
Fresh waterFresh waterFresh waterFresh waterFresh waterFresh waterFresh waterFresh waterFresh waterFresh water
A1(NO3)3A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
A1(NO3)3
6750675067506750675067506750675067506750
Time(hr)
35
10.525
PH
UnbufferedUnbuffered
UnbufferedUnbufferedUnbufferedUnbuffered
Effect
All cells deadAll cells dead
All cells deadAll cells deadAll cells deadAll cells dead
5
72-144192-264
192312
<2431272-288
172-240>24048
Unbuffered
UnbufferedUnbufferedUnbufferedUnbufferedUnbufferedUnbufferedUnbufferedUnbufferedUnbufferedUnbuffered
All cells dead
All cells deadAll cells deadAll cells deadAll cells deadAll cells deadAll cells deadAll cells deadAll cells deadAll cells deadAll cells dead
Ref.
7979
79797979
79
79797979797979797979
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Alga Medium
Chlorococcales
Chlorella pyrenoidosa(aluminum tolerant)
Scenedesmus quadricaudaChlorella vulgaris
Chlorella sp.
Ulotrichales
Ulva lactuca Sea water
TABLE 8 (continued)
Effect of Aluminum on Algae
AgentAl concentration
(mg/1)
Fresh water
River HavelModified
Biejerinck'sTamii mineral
A1,(SO4)3
A1C1,A1,(SO4)3
Al,(SO4) a
A1C1,
48
1.5-2ca.320
<3050
Time(hr)
360
96672
PH
4.6
Effect Ref.
A1C1, 0.2 216 8.2
13% growth inhibition 80
Toxicity threshold 38ca. 50% growth 81inhibition
No effect 8280% growth inhibition 82
33% growth inhibition 83
c3
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circumstances which favored the ability to toleratehigh concentrations of metals freshly leached fromadjacent rocks and soil.
TOXICITY TO HIGHER PLANTS
It is known that aluminum affects the uptakeand transport of phosphorus86 '87 and calcium80
in terrestrial plants and is generally more toxic inacid soils, although resistance to aluminum intoxi-cation varies widely among species. In a study oftwo terrestrial plants grown in water culture,Hackett88 found that growth of the grass Des-champsia flexuosa is stimulated by 4 mg Al perliter, while growth of Lolium perenne is inhibitedby aluminum at the same level at pH 3.8 to 3.9. Itis significant that growth inhibition in Lolium isgreatest at high phosphate levels, indicating thatthe mechanism of aluminum intoxication involvesmore than simple deprivation of phosphorus.
A few studies record the effects of solublealuminum on aquatic angiosperms. Stanley89 hasfound that the root weight of Asian watermilfoil(Myriophyllum spicatum) rooted in soil or ferricsilicate substrate is inhibited by 50% at an alumi-num concentration of 2.5 mg/1 in the water (pHand counterion unspecified). The same amount oftoxicant added to the soil instead is significantlyless inhibitory. The influences of high acidity andaluminum on the growth of lowland rice have beenstudied by Thawornwong and Van Diest,90 whohave reviewed the literature through 1973. Theyreport that the presence of aluminum in concen-trations of 0.05 and 0.2 mg/1 in the nutrientsolution during the seedling stage inhibits growthby 40 to 50%. Concentrations ten times higher arelethal to seedling rice, but not harmful to moremature plants. The growth of either is unaffectedby pH levels of from 3.5 to 5.0.
A colony of the evergreen shrub Empetrumnigrum (black crowberry) growing on a peat raft inWybunbury Moss, Cheshire, England has beenobserved to decline during periods of high water.Speculating that the high soluble aluminum level(0.05 mg/1) measured may contribute, Bell andTallis9' have cultured E. nigrum seedlings in thepresence of various levels of aluminum sulfate inwater at pH 4. A reduction of 50% in shoot dryweight was caused by aluminum ion at a concen-tration of 0.05 mg/1. Seedlings subjected to 5 mg/1declined further, but were still alive after 15weeks. If the soluble aluminum in Wybunbury
Moss was, in fact, responsible for the die-off of E.nigrum, it is interesting to note that the mostcommon associates, Erica tetralix (crossleafheath), Eriophorum angustifolium (narrowleafcottonsedge), E. vaginatum (sheathed cotton-sedge), Vaccinum oxycoccus (small cranberry),Sphagnum recurvum, and Aulacomnium palustrewere unaffected, as were two aquatic species ofthe surrounding reedswamp, PfcragTmres communis(common reed) and Typha latifolia (commoncattail).
Bohm-Tiichy's79 study on the effects of im-mersion in aluminum nitrate solutions on sub-sequent cell plasmolysis includes data for theleaves of several flowering plants. Upper epidermalcells are destroyed only on prolonged exposure tosolutions containing 10 mg Al per liter, demon-strating at least a moderate degree of resistance tosoluble aluminum. Comparative aluminum toler-ances are difficult to evaluate because cell survivaltimes are relatively insensitive to variations inconcentration over the range studied.
ALUMINUM POLLUTION INNATURAL WATERS
Experiments have been heretofore describedrelating the toxicity of aluminum to aquaticanimals under controlled laboratory conditions. Inmany respects, more meaningful indications of thetoxic effects of a pollutant are gained by carefulexamination of the fauna of the receiving waterscompared with identical but unpolluted waters, aprocedure formulated in terms of diversityindices.92 Carter93 has studied the bottom faunaof streams in the Beaver Creek basin of Kentucky,many of which are subjected to pollution fromacid mine drainage. Soluble aluminum levels maybe as high as 85 mg/1 in the Cane Branch, and themacroinvertebrates and Amphibia of the CaneBranch are far poorer in numbers and diversitythan those of the relatively unpolluted HeltonBranch. Similarly, Smith94 has reported that theindigenous fishes of the region, including creekchub and bluegill, are dead within 3 hr after beingcaged in the Cane Branch. Unfortunately andinevitably, high soluble aluminum levels are ac-companied by low pH levels (frequently below pH3), so that the toxicity of aluminum cannot beindependently evaluated.
Recent concern in Europe has led to investi-
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gation of the ecological consequences of marinedischarge of large volumes of "red mud," a highlyalkaline by-product in the recovery of aluminafrom bauxite by the Bayer process. Red mud maycontain as much as 32% alumina, depending on theorigin and treatment of the bauxite, together withsignificant proportions of silica, titania, and ferricoxide. The effects of suspended and settled redmud on marine organisms has been reviewedthrough 1972 by Dethlefsen and Rosenthal95 andBlackman and Wilson.96 Exposure of a variety ofmarine organisms including pelagic and bottomfishes, pelagic and benthic macroinvertebrates, andherring roe and fry97 indicates that the injuriouseffects of red mud are reversible and result fromadhesion of the mud to body mucous, gills, andvarious structures of the feeding mechanisms andalimentary tract rather than from any specifictoxic effect of aluminum. The most sensitiveorganism investigated is the marine planktoniccopepod Calanus helgolandicus, for whichPaffenhofer98'99 has found that growth rates andviability of juveniles are reduced by suspended redmud at levels of 1 to 10 mg/1. He proposes that theadverse effects are the result of ingestion of redmud and consequential diminished food intake.Halsband and Halsband100 have shown that redmud has an adverse effect on the populationdynamics of Dunaliella euchlora and a Protococcusspecies when present at a level of 1 to 5 g/1.Filtered material is largely without effect on thealgae, suggesting that growth inhibition is due tophysical effects of the mud, such as light restric-tion. Rosenthal, Dethlefsen, and Tiews101 con-clude from these various studies that pro-tection of flatfish stocks and benthic faunarequires that red mud be discharged at depths noshallower than 3000 m. On the other hand,Peres102 asserts that a 6-year survey of a red muddumping ground shows no environmental damageto the bottom at 340 m.
There is no clear evidence for aluminum intoxi-cation of mammals drinking polluted water. Ebenset al.103 have reported a case in which beef cattlesuffered a serious metabolic disorder whenpastured at a Missouri claypit with a total alumi-num content of 13 mg/1 and a pH of 4.3. Otherminerals in unusually high concentrations wereberyllium, cobalt, copper, nickel, and zinc. Thecattle exhibited symptoms of mineral imbalance,but it is not known whether the cause was thewater or the forage.
THE CHEMISTRY OFALUMINUM IN WATER
The chemistry of aluminum in water is es-sentially the chemistry of aluminum hydroxide,which differs from the hydroxides of othernontransition metals in the following three impor-tant respects:
1. It is readily amphoteric.2. It forms complex ions with other sub-
stances present in the water.3. It tends to polymerize.
Thus, the form and concentration of aluminum inwater depends on the pH and the nature ofsubstances dissolved in the receiving waters and, toa lesser extent, on the temperature and theduration of exposure to the water. The followingexposition, which is adopted from the work ofHem and colleagues,104"109 Brossett,110 Brossettet al.,111 and Turner,112 is applicable to dilutesolutions of the type most common in naturalenvironments.
Monomeric Aluminum HydratesWhen an aluminum salt of a noncomplexing
acid (such as aluminum perchlorate) is dissolved inpure water, it dissociates to form an aluminum iongenerally considered to be six-coordinated withwater molecules, A1(H2O)63+. Solutions of thealuminum ion are acidic because of the hydrolysisequilibrium
+ H2O = A1(H2O)S OH2* + H3O+
Omitting coordinated water molecules for reasonsof economy, the mass law becomes
K, =[A1OH2+][H*|
The value of Ki has been determined inde-pendently by several investigators to be 10 "s at25°C. Thus, a solution of 10 "3 M aluminumperchlorate in pure water will have an initial pHvalue close to 4. This is important to considerwhen evaluating the toxicity of aluminum com-pounds, because the lethal limit for many aquaticorganisms occurs at pH > 4.
Progressive hydrolysis of the aluminum ionleads to the univalent ion and, finally, colloidalaluminum hydroxide, as follows
June 1977 183
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A1OH2+ + H2O = A1(OH)%
Al(OH)+2 + H2 O = A1(OH)3 + H*
v [A1(OH)\][H+]
maintain 2 X 10toxicity studies.
M aluminum at pH 9 for their
K3
[A1OH"1
[Al(OH)+2 1
In basic solutions, aluminum hydroxide exhibitsits amphoteric nature by conversion to the alumi-nate anion
A1(OH)3 + H2 O = Al(OH) % + H*
K B =[A1(OH)-J[H + ]
Aluminate ion represents the apparent limit for2 -
Polymeric Aluminum HydratesThere is a strong tendency for dissolved alumi-
num to form dimeric, oligomeric, and polymericspecies. This tendency is enhanced as the ratio ofaluminum-bound hydroxide to aluminum increasesfrom 0 to 3. Removal of a proton from thehexacoordinate aluminum cation A1(H2O)6
3+ givesthe bivalent cation A1(H2O)SOH2+, for which theOH:A1 ratio is 1. Dimerization of this cationproceeds with loss of two molecules of water togive A12(OH)2 X (H2O)8
4+, a pair of octahedronswith a shared edge (Figure 3). Three dimers maynow combine in ring formation as follows
hydrolysis of Al3+; the species A1(OH)S2" and 3A12(OH)2(H2O)2+ - A16(OH)12(H2O);*2 + 6H,O+
A1(OH)63 " have not been reported. Table 9 lists
equilibrium data for aluminum in water, andFigure 1 illustrates the distribution of monomericaluminum species as a function of pH. Data pointsfor Figure 1 were derived for aluminum inequilibrium with crystalline (stable) aluminumhydroxide at an ionic strength of 10 "2 . Thesolubility of aluminum in pseudoequilibrium withcolloidal or microcrystalline (unstable) aluminumhydroxide shown in Figure 2 is higher, whichexplains Freeman and Everhart'sI4)2s ability to
For this hexomer the OH:A1 ratio is 2. Combi-nation of many such hexomers in parallel sheetsresults in construction of the mineral gibbsite,which has an OH:A1 ratio of 3, corresponding toelectrical neutrality. It is important to recognizethat the dimers and higher oligomers of aluminumare kinetic, rather than thermodynamic, species.The true equilibrium is represented by Figure 1,with monomeric species in equilibrium withcrystalline A1(OH)3. There is disagreement on the
TABLE 9
Equilibrium Constants at 25° C
Equilibrium
A10H" + H2O = Al(OH)2+ + H*
A1(OH)2 + + H2O = A1(OH)3
A1(OH)3 +H 2 O = A1(OH)4"
A1F3
F"=A1F3? - = AlF4"
A1SO4+ + SO4
2" = A1(SO4)2 "2A13+ + 2H4 SiO4 + H2 O = Al2 Si, Os (OH)4 + 6H*2A1(OH)4 " + 2H4 SiO4 + 2rT = Al2 Si, Os (0H)4 +
7H2O
aDerived from data presented.bIn equilibrium with bayerite.cIn equilibrium with fresh precipitate.
Equilibrium constant Ref.
1.0 X 10 "1.7 X 10 -' a
0.35 X 102
1.11 X 10"14 b
1.93 X 10"13 c
1.05 X 10'5.5 X 10s
1.86 X 104
5.0 X 102
15.50.91.6 X 103
805.25 X 1 0 " *9.55 X 1032
108108108105105106106106106106106113113109109
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10"
-HE
RP
ER
L
COLU
i
O
ION
, 1JT
RA
TI
CO
NC
EIT
10"4
10" 5
10"6
10 ' 7
i-810
FIGURE 1. Solubilities of monomeric aluminum species at 25° C as a function of pH. (FromSmith, R. W. and Hem, J. D., U.S. Geol. Surv. Water Supply Pap., No. 1827D, 1972.)
FIGURE 2. Solubility of microcrystalline gibbsite at 25°C as a function of pH.(From Roberson, C. E. and Hem, J. D., U.S. Geol. Surv. Water Supply Pap.,No. 1827C, 1969.)
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FIGURE 3. Structure of the dimeric cation A1,(OH)2(OH2), *4. (From Hem,
J. D. and Roberson, C. E., U.S. Geol. Surv. Water Supply Pap., No. 1827A, 1967.)
structures of the intermediate hydrates. Matijevicet al.114 and Matijevic and Stryker115 havepresented evidence that the first hydrolysisproduct of aluminum nitrate has a bound OH:A1ratio of 2.5 and a charge of +4, corresponding toA18(OH)20
4+.According to Smith and Hem108 and
Smith,116 when hydroxide is added to a solutionof an aluminum salt in a quantity sufficient toprovide a bound OH:A1 ratio of 1 to 3, a portionof the aluminum will begin to polymerize. Within24 hr the concentration of monomeric aluminum(A13\ A10H2+, A1(OH)%, and A1(OH)4 ") will havestabilized, while polymeric aluminum hydroxide isgradually converted to larger units. Gibbsite parti-cles appear after a few days at 25°C (for OH:A1ratios of 2 to 3), but complete crystallization maytake a year or longer, although the process isconsiderably accelerated at 40°C. ' ' ' During thistime, the pH will drop slightly as bound hydroxidebecomes more intimately incorporated into thebuilding crystal structure. Thus, it is seen that anorganism in contact with a freshly preparedsolution of aluminum (buffered or partly buf-fered) may be exposed to a spectrum of hydratedaluminum species (monomeric and polymeric)with different toxic potentials. An aged solutionmay exert a different order of toxicity due tolower concentrations of monomeric species andabsence of intermediate polymers. Had Freemanand Everhart14 '2 s aged their aluminum hydroxidesolutions for a few days before conducting
toxicity studies with rainbow trout, their resultsmight have been substantially altered.
Complex IonsAluminum is capable of forming strong
coordinate bonds with substances other than waterand hydroxide. Al3+ forms six different com-plexes with fluoride ion, the stability constantsfor which are presented in Table 9. If oneconsiders only the first equilibrium, for which Ki= 107, it is readily shown that a solutioncontaining 10"4 M aluminum (2.7 mg/1) and 10"4
M fluoride (1.9 mg/1) would contain only 3 X10~6 M (0.08 mg/1) uncomplexed aluminum. Themineral cryolite (Na3AlF6) is slightly soluble inwater; at saturation, it provides a solution con-taining about 50 mgA of aluminum, virtually all ofwhich is complexed by fluoride.117 Apparently,the similar formation of chloride complexes inwater is not important.
The stability constants for aluminum sulfatecomplexes are much smaller than those for fluor-ide complexes, as shown in Table 9; but, becausesulfate is a much more important constituent ofmost natural waters, sulfate complexes may be asprevalent as fluoride forms. In a solution con-taining 10"4 M aluminum (2.7 mg/1) and 10"3 Msulfate (96 mg/1), the concentration of un-complexed aluminum would be approximately0.038 X 10"3 M (1.0 mg/1). Where several dif-ferent ligands compete for aluminum, thedistribution of aluminum species will depend on
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u.
O
-1
-2
-3
-4
-5
-6
-7
-8
F complexes predominate /
0.000001 /
OH complexes predominate
4
-10
5
-9
6
-8
7PH
-7
LOG [OH]
8
-6
9
-5
10
-4
FIGURE 4. Ratio of free aluminum activity to total dissolved aluminum as a function offluoride and pH (zero ionic strength). (From Hem, J. D., U. S. Geol. Sun. Water Supply Pap.,No. 1827B, 1968.)
the concentration of each and on the pH. Hem106
and Roberson and Hem107 have prepared graphsfrom which it is possible to derive levels of freeand complexed aluminum for various combi-nations of aluminum, fluoride, sulfate, andhydroxide and different ionic strengths.
More than one ligand may combine in the samecomplex. For example, Matijevic and Stryker11 s
have presented evidence for the existance ofA18(OH)1O(SO4)S
4+ in aluminum sulfate solutionswith pH ca. 5.
Insofar as complexing ligands such as fluorideand sulfate are present in water, they will increasethe amount of dissolved aluminum in equilibrium
with solid aluminum hydroxide. In Figures 4 and 5the effects of dissolved fluoride and sulfate on thesolubility of freshly precipitated aluminumhydroxide are demonstrated for different pHlevels.106 It is seen that the concentration ofdissolved aluminum is increased significantly onlyat sulfate concentrations above 10 ~3 M. Forfluoride, on the other hand, the increase insolubility of aluminum hydroxide is importantbelow 10~5 M in moderately acidic solutions. Forboth ligands, enhancement of solubility is insigni-ficant at high and low pH where aluminumhydroxide is already moderately soluble. In mostnatural waters with pH 6.5 to 8.5, neither fluoride
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u
- 1
8 _2C3O- J
- 3
-4
i / '
S04 complexes predominate
0.001 /
10.01 /
- - //
0.10 //
/ •/
/- 0.5 /
—A/// i
<
i
OH complexes predominate
7
pH
10
FIGURE 5. Ratio of free aluminum activity to total dissolved aluminum as afunction of sulfate and pH (zero ionic strength). (From Hem, J. D., U. S. Geol.Surv. Water Supply Pap., No. 1827B, 1968.)
nor sulfate will be present in significant concen-tration to enhance the solubility of aluminumhydroxide.
Dissolved silica is also in competition foraluminum in natural water. Hem et al.109 haveexamined the synthesis of halloysite, Al2 Si2 Os
(OH) 4 (H 2 O) X , from solutions containingaluminum and silicic acid at various pH levels.Equilibriums and equilibrium constants for acidand basic solutions are presented in Table 9. Silicicacid has the curous property of inhibiting crystal-lization of aluminum hydroxide, further il-lustrating the fact that the chemical form alumi-num takes is affected in many subtle ways by theproperties of the receiving water.
The nature of the complex ions formed fromaluminum salts and phosphoric acid is imperfectlyunderstood. Callis et al .1 '8 have reviewed thechemistry of polymeric aluminum orthophos-phates, for which the stability and degree ofaggregation are greatly dependent upon the pH ofthe medium. By precipitation with phosphoricacid at pH 5, Chen et al .1 '9 have isolated a solidto which they assign the formula Ali3(OH)30
(H2PO4)9(H2O), g and a structure consistent withthe gibbsite formulation. The most stablecompound of aluminum and phosphoric acid ispresumably A1PO4, for which the handbook valueof the solubility product is 6.3 X 10" ' 9 .
The solubility of aluminum in water is en-
hanced manyfold by synthetic chelating agentssuch as ethylenediamine tetraacetic acid (EDTA),nitri lotriacetic acid (NTA), and sodiumtripolyphosphate (STPP). The presence of theseagents in wastewater effluents could greatlyelevate the concentrations of soluble aluminum inreceiving waters. This effect would usually belimited to the region of discharge, as EDTA, NTA,and STPP are all biodegradable to some extent.
The physical chemistry of turbidity reductionusing aluminum compounds is a highly complexsubject involving the interrelation of temperature,turbulence, particle size, pH, and concentrationsof many ions, including aluminum sulfate andorthosphosphate. This subject will not be dis-cussed further in this report except to note thatthe forms of aluminum present in turbid watersmay be quite different from those present in clearwater.
Natural Organic ComplexesMany organic materials of natural origin are
capable of mobilizing aluminum in the soil. Theseinclude humic and fulvic acids from decay of thelitter mat and a mixture of polyphenols, reducingsugars, and organic acids present in forest canopydrip.120 The role of organics in mobilizingpolyvalent metals in some coastal plain rivers ofthe southeastern United States has been discussedby Beck and Reuter,12 ' who present evidence for
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significant enhancement of aluminum levels inwaters of high organic content. They note thathumic substances probably occur in solution asmicrocolloids, which are subject to aggregation,flocculation, and precipitation. Thus, theconcentration of organoaluminum complexes in asample of natural water may diminish with time,whether or not the organic moiety is biodegraded.
DETERMINATION OFALUMINUM IN WATER
Two types of procedures are used for aluminumanalysis. One measures all the aluminum in aparticular sample, while the other measures onlythe aluminum in a certain chemical form (such asthe monomeric ion). Many instrumental proce-dures, such as emission spectroscopy and neutronactivation, lie in the first category; colorimetricmethods and polarography fall into the second. Atthis time, no single procedure seems to have gainedgeneral acceptance. On the basis of a check-sampleprogram, McFarren and Lishka122 stated in 1968that "no satisfactory procedure exists for alumi-num."
Sample PretreatmentWhere natural water samples are routinely
filtered and acidified before analysis, the measuredsoluble aluminum concentration may depend onthe type of filter used and the length of time thesample is allowed to stand after acidification. Theeffect of filter pore size on the analysis ofaluminum in water has been studied by Kennedyet al.123 who have reviewed earlier work. Theyreport that sufficient fine-grained material can pass0.45 and 0.22 [xm membrane filters to introducelarge positive errors and recommend the use of 0.1Aim filters. More recently, Wagemann andBrunskill124 have presented evidence that a silvermetal membrane filter gives more completeremoval of particulate matter than a celluloseacetate membrane filter of the same pore size.Materials which adsorb aluminum ions can intro-duce negative errors; Shull and Guthan12S havefound that glass wool, absorbent cotton, and mostpaper filters remove much of the soluble alumi-num in water samples.
Colorimetric MethodsColorimetric procedures exploit a property of
aluminum salts long known in the dyeing industry:the ability to form brightly colored, insoluble"lakes" with certain dyestuffs. Colorimetricmethods for determining aluminum have beenreviewed by Sandell126 and in part byPackham,127 Giebler,128 and Dougan andWilson.129 A method in common use is based onthe ammonium salt of aurintricarboxylic acid, atriphenylmethane dye known as aluminon, whichcombines with the aluminum ion to give a deepred color. The test is carried out at pH 4 and isspecific for monomeric aluminum ions; however,low-molecular-weight oligomers of aluminumhydroxide which are readily converted to mono-meric ions will also be detected. The detectionlimit is approximately 0.02 mg/1. Substanceswhich react with aluminum (such as fluoride andpolyphosphate) and substances which react withaluminon (such as iron) interfere with the test. Amodified procedure by Shull,130 later incor-porated into the 12th edition of StandardMethods,131 uses thioglycolic acid to eliminateiron interference. Fluoride can be removed byevaporating an acidified sample almost to dry-ness,132 or the interference can be eliminated bytreatment with Th(NO3)2.133 Hot acid treatmentalso eliminates interference from silica and poly-phosphate.13 4 Chromium interference has beenremoved by oxidizing Cr3+ to Cr6+ and passing thesample through an ion exchange column.13 s Rolfeet al.,136 who have surveyed many potentialinterferences, have stated that anions and cationsnormally present in water do not interfere in thealuminon procedure. Regardless of interferences,the procedure calls for boiling the samples for 15min prior to reading the color intensity at 525 nm.All investigators agree that a standard curve mustbe prepared for each batch of aluminon tocompare known and test samples, because Beer'slaw is not followed over much of the concen-tration range. Procedural data for a number ofcolorimetric tests are summarized in Table 10.
Because the aluminon procedure is complicatedand time consuming, the 13th edition of StandardMethods13"7 tentatively specified the Erio-chrome® cyanine R method adopted by Shull andGuthan12s from the procedure of Knight.138
Eriochrome cyanine R, a triphenylmethane dyealso known as Solochrome® cyanine R, produces ared aluminum complex with an absorption maxi-mum at 535 nm and is more sensitive than
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TABLE 10
Colorimetric Methods for Determination of Aluminum in Water
Dye
Aluminon
Eriochrome® cyanine R
Hematoxylin
Alizarin red SFerron(Pyro)catechol violet
StilbazoChromazurol S8-Hydroxyquinoline
Vax o f
complex(nm)
525
535
620
480370585
500545
~400
Range(mg/1)
0.02-1.0
0.006-0.5
0.01-0.5
0.02-0.5
0.005-0.20.005-0.70.007-0.2
ca. 0.005-1.20.004-0.04
OptimumPH
3.7-4
6
7.5
5.9-6.26.1 ±.1
5.65.8
Interference
Fe,Cr,Ti,F,S<V-,PO43-,
polyphosphate, Ca (>143 ppm),Clj (>0.5ppm), SiO4
4"Fe, Mn, F, polyphosphate,
Si<V'(>80ppm)Mg,Ca,PO4
3-Fe, Mn, Cu (0.2 ppm), F (>5 ppm),Ca (>300 ppm CaCO3), Mg,(>150ppmCaCO3)
Fe, Mn, F, PO4 3", Ca
Fe, Cu, FF,PO4 '"(slight)Fe(slight)F (large)Be, Zr4\ Th4+, FNone, common industrial water
Ref.
126-128, 130-136
125,126, 128, 129
128126-128, 141-144
126-128, 145, 146116, 147129148129146,149112, 126, 150,151
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aluminon. The interference of iron and manganeseis eliminated by addition of ascorbic acid. Theprincipal negative interferences, fluoride andpolyphosphate, can be eliminated as describedabove for aluminon. Where the concentration offluoride is known, correction can be made byaddition of fluoride to the standards; StandardMethods13 7 provides a graph for fluoride correc-tion. Silica does not interfere below 80 mg/1.13 9
The toxic heavy metals interfere only whenpresent in much higher concentrations than alu-minum.140 Although the Eriochrome cyanine lakeobeys Beer's law over a wider range, a standardcurve is still required. In disagreement with otherinvestigators, Giebler128 states that the erio-chrome cyanine method is time-consuming andunsuitable because of the many interfering ions,including calcium and magnesium.
For determination of total aluminum andaluminum ion in water, the American Society forTesting and Materials (ASTM)141 specifies thehematoxylin method, adopted from the procedureof Strafford and Wyatt.142 Hematoxylin (anatural dyestuff derived from heartwood)produces a blue lake with aluminum, but the colormay be modified by that of excess dye. The ASTMprocedure requires extraction of interfering ironwith ammonium thiocyanate. In a simpler pro-cedure by Houghton,143 '144 iron is masked bypotassium cyanide. Traces of manganese andcopper may also interfere, and the color ismodified by larger amounts of calcium andmagnesium. Fluoride is tolerated up to 1 mg/1. Thecolor obeys Beer's law up to approximately 0.1mg/1,127 and the detection limit is 0.01 to 0.02mg/1.
Alizarin red S, an anthroquinone dye, has beenused for determination of aluminum in organicmaterials, but it is also acceptable for analyzingwater samples. It forms a deep red lake, Xmax 480nm, which obeys Beer's law up to 0.5 mg Al perliter.127 Iron and manganese interference can becancelled using citric acid. Giebler12 8 notes thatthe procedure is quite sensitive to fluoride inter-ference. Packham127 suggests that the AlizarinRed method would be well-suited for field analysisof water samples, as boiling of the solution is notrequired.
Ferron, an 8-hydroxyquinoline derivative,reacts with aluminum to give a complex whichadsorbs at 370 nm.148 Interference from iron is
eliminated by complexing with orthophenan-throlene, and beryllium minimizes fluoride inter-ference. Smith116 has used this procedure becauseit permits distinction among the three forms ofaluminum present in water: monomeric, low-molecular-weight polynuclear, and microcrystal-line or colloidal. Monomeric and polynuclearaluminum is measured by waiting until colordevelopment is complete; the monomeric speciesare determined by extrapolating color develop-ment to zero time. The ferron method, which wasused by Freeman and Everhart14>2S in toxicityexperiments, is well-suited for aluminum levels inexcess of 1 mg/1. Ferron is also employed in acurrent ASTM procedure.1418
Dougan and Wilson129 have developed amethod using (pyro)catechol violet which theyhave found to be superior to methods based onEriochrome cyanine R or stilbazo. The sensitivityis better and interference by fluoride at 1 ppm ismuch less important. Beer's law is obeyed over arange of aluminum concentrations, and a singlecalibration is adequate for many batches. Of thecommon wastewater constituents, only poly-phosphate offers significant interference. Themethod calls for pretreatment of samples withhydrochloric acid, which, they note, may convertall forms of aluminum into those which react withcatechol violet.
Panovsky146 has described a fluorimetricprocedure based on the complex of aluminumwith morin (a natural flavone) as well as twocolorimetric procedures suitable for determinationof low levels of aluminum in treated drinkingwater and boiler feed-water.146 The fluorimetricmethod is said to achieve a variance of less than20% at an aluminum concentration of 0.005 mg/1and is employed by ASTM in a current proce-dure.14 l a A fluorimetric method based on sodium2-quinizarinsulfonate has also been described.152
Several investigators have determined aluminum insea water by the fluorescence of the complexformed with Blue-black R at pH 5, using anexcitation wavelength of 367 nm and an emissionwavelength of 603 nm.1 s 3" ! s s iron interference iseliminated with orthophenanthrolene and a detec-tion limit of better than 0.002 mg/1 is claimed.1 s 3
For very low concentrations of aluminum, pro-cedures have been devised to extract the aluminumas the 8-hydroxyquinoline complex with chloro-
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form and determine the quinolinate in chloroformsolution either spectrophotometrically15O)lsl orfluorimetrically.156'157 Aluminum is also ex-tractable as the cupferronate.128
Instrumental MethodsThe 13th edition of Standard Methods1 Si
specifies the atomic absorption procedure fordetermination of aluminum in water. Direct deter-mination using a Boling burner and a nitrousoxide-acetylene flame provides an absorptionmaximum equal to 1% of full scale at 309.3 runfor an aluminum concentration of 1 mg/1. Toachieve a detection limit in the 0.01 to 0.05 mg/1range, aluminum is complexed with 8-hydroxy-quinoline at pH 8 and extracted with a minimumvolume of chloroform,1 S 8 benzene,159 ormethyl-isobutylketone.160 No ions interfere significantlyexcept magnesium, which may complex with8-hydroxyquinoline and coprecipitate alumi-num.1 6 0 However, this is a slow reaction, and thealuminum can be recovered quantitatively by rapidextraction. Recent studies161 '162 have shownthat atomization from graphite surfaces canenhance the detectability of aluminum by severalorders of magnitude, thereby permitting directanalysis of samples containing trace levels ofaluminum without prior concentration.
The three spectrochemical approaches to thequantitative analysis of aluminum and other minorelements in natural waters16 3 are
1. Direct sparking of a water sample orpartially evaporated water sample.
2. Direct arcing of the residue obtained byevaporating the sample to dryness.
3. Separation of the minor elements bychemical precipitation and subsequent arcing ofthe ashed precipitate.
In the first procedure, a water sample isconcentrated 10- to 100-fold by evaporation.After addition of an internal standard, the con-centrate may be sparked in a porous cup electrode,with the spectrum recorded on photographicfilm.164 Emission lines at 2652, 2660 or 3082 Amay be used. More recently, Kopp and Kroner16S
have described a direct-reading spectrochemicalprocedure using a rotating disc high-voltage sparktechnique which permits analysis of water samplescontaining 0.01 to 0.8 mg/1 of aluminum. In the
second method, the dry residue is mixed with oneor more times its weight of powdered graphite andeither put into an open cup electrode166 orcompressed under ultrahigh pressure into abriquette.167 The detection limit for aluminumby either procedure is between 0.1 and 1 mg/1,although LeRoy and Lincoln168 have recentlyreported detection of 0.01 mg/1 with relativestandard deviation of 7.3% using the 3082.15 Aline of aluminum and a germanium standard. Inthe third method, trace materials are precipitatedfrom the water sample by 8-hydroxyquinolineaided by tannic acid and thionalide at pH 5.2, asdescribed by Silvey163 and SUvey andBrennan.169 The precipitate is collected by filtra-tion, ashed, and analyzed as described above forresidues. The authors do not quote sensitivitiesdirectly, but the detection limit appears to beapproximately 0.01 mg/1 for aluminum. Russianworkers,1 7 0 using an AC arc, claim sensitivity ofat least one order of magnitude better with thesame general procedure. The spectrographicmethod is time-consuming, but it permits analysisfor many trace metals simultaneously. McFarrenand Lishka122 report that a 0.5 mg/1 samplecirculated among four laboratories using spectro-graphic analysis produced a relative error of 52%.
Podobnik et al.171 have described a flamephotometric procedure. The water sample istreated with cupferron and extracted with4-methyl-2-pentanone. The organic extract isanalyzed at 484 nm by means of an oxygen-hydrogen atomizer-burner. The detection limitappears to be better than 0.05 mg/1.
Several studies1 7 2 '1 7 3 suggest that polarog-raphy may provide a sensitive tool for wateranalysis. Maienthal and Taylor172 have reviewedmethods for determination of trace inorganics inwater; cathode ray polarography is claimed to givedetection limits in the microgram per liter rangefor aluminum in reactor water.
Spark-source mass spectrometry is a promisingtool for trace metal analysis; the work of Wahlgrenet al.174 suggests a theoretical detection limit ofapproximately 0.0001 mg/1 for aluminum inwater.
Neutron activation is a sensitive method foranalysis of many trace metals. When 27A1 issubjected to a flux of thermal neutrons it isconverted to the radioactive species 28A1, with adecay half-life of approximately 2.5 min. Samples
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may be analyzed directly, or the metals may beconcentrated by precipitation. Fujinaga et al.17S
have isolated trace metals by reaction with8-hydroxyquinoline and coprecipitation witho-phenylphenol. The precipitate is irradiated for afew minutes under a high thermal neutron fluxand the induced radioactivity is analyzed by X-rayspectrometry, using a Ge (Li) detector. Themethod is sensitive to 10"s mg Al/1, but alumi-num impurities introduced by glassware, etc.,raise the practical detection limit to 0.001 mg/1-Furr and Mooney176 have analyzed water samplesdirectly with a precision of 0.03 to 0.1 mg/1.Pelekis et al.1 7 7 have placed the limit of detectionfor aluminum at 0.09 fxg.
Miscellaneous MethodsAlthough chromatographic techniques have
found limited application to analysis of aluminumin water, they may be particularly suitable fordifficult samples. For example, Quentin178 hasanalyzed mineral waters of high aluminum contentusing paper chromatography. The sample isevaporated and the residue is purified by solutionin acid and reprecipitation of the hydroxides. Theprecipitate is chromatographed after solution inacid and developed with aluminon. Developedspots corresponding to about 5 ng of aluminumare cut out and extracted with acid. The extractedaluminum is analyzed spectrophotometrically asthe aluminum complex, with a precision of 5% orbetter. Yamane et al.1 7 9 have derived a procedurefor determination of aluminum by thin-layerchromatography (TLC). Aluminum is extractedfrom the sample as the 8-hydroxyquinoline com-plex with chloroform and back-extracted into 3 TVHC1, which is then applied to the TLC plate.Development with 8-hydroxyquinoline permitsdetection of aluminum at the 0.1 mg/1 level. Aprocedure employing gas-liquid chromatography(GLC) has been devised by Lee and Burrell.180
The aluminum in a sea water sample is extractedwith trifluoroacetylacetone in toluene. GLC of theextract, using an electron capture detector, per-mits detection of aluminum at the picogram(10~12 g) level, indicating detection limits inwater of better than 0.001 mg/1.
Several workers181"183 describe complexi-metric procedures for aluminum without reportingsensitivities. Typically, the sample containingaluminum is treated with an excess of a com-
plexing agent such as EDTA, and the excess isback-titrated with Cu2+, Zn2+, or Pb2+ ion in thepresence of a metal-detecting indicator such asdithizone. This method seems unlikely to provideeither sensitivity or selectivity adequate for analy-sis of aluminum in natural waters.
There is probably no one method of aluminumanalysis best suited for all water samples. Wherethe equipment is available, the atomic absorptionprocedure described in Standard Methods1 s& isrelatively simple and sufficiently accurate for mostpurposes. For routine colorimetric analyses, theEriochrome cyanine procedure of StandardMethods131 is simple and fairly precise, while theferron technique, although not so sensitive,permits distinction of different forms of alumi-num.116
ENVIRONMENTAL PREVALENCEOF AQUATIC ALUMINUM
Although many seas, lakes, rivers, springs, andwells have been analyzed for their trace metalcontents, relatively few aluminum analyses havebeen performed. Tables 11 to 16 list data forterrestrial surface and subsurface waters sampledthroughout the world; Table 17 lists data foroceans and seas. For many references, a body ofdata has been condensed into a single entry. Forexample, where the U.S. Geological Survey hasprovided analyses for many streams in a singlewatershed at various sampling stations and times,Table 11 lists only the range of aluminum valuesdetermined if it appears that variations at any onesampling point will be as great as the variation overthe whole watershed.
Two factors concerning the stated aluminumlevels are noteworthy. Previous sections on thechemistry and analytical chemistry of aquaticaluminum indicated that there is no clear distinc-tion between dissolved and suspended aluminum.Some filters pass microcrystalline or colloidalaluminum hydroxide, while others absorb much ofthe soluble aluminum. Many investigators nowarbitrarily use a 0.45 jum millipore filter todistinguish between dissolved and particulatealuminum. For much of the data in Tables 11 to16 the state of the sample is unknown, although itis presumed to be soluble. The second point is thatreliable procedures for trace analysis of aluminumhave only recently become available, and most of
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8Location8
I
TABLE 11
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
Water type
AlabamaMontgomeryBirmingham
Alaska
ArizonaPhoenix
Arkansas
CaliforniaFresno
WellRiverMobile RiverWell, Eutaw clay
NaCl-CaCl2 springYukon River
RiverColorado River
Sandstone springWell, shaleHot spring
WellSurfaceWellRiverSpringWell, oil field brineStreamSacramento RiverSpring, gneissOil field brineBrine springWarm brine springBrine springNaCl-CaCl, spring
PH
7.27
7.7
7.1
7.8
7.446.5
7.5
8.17.58.47.26.79
Al content(mg/1)
0.0830.0430.1863.6
0.2• <0.082
0.1300.012
0.2280.9
0.062<0.05-1.2<0.02-8.50.0002-0.00057-0.243
0.06-0.600.40.40.90.30.20.04-0.3
Mean
(0.6)(0.71)(0.0003)(0.030)(0.038)(0.015)
Methodb
spspsp
sp
Datec
19581952
19561959
195419551956
195919591959
1956-1958195519551955194919561956 •
R
184184185186
186185
184185
186186186
184187187
188188188185186186186186186186
a City listings indicate municipal water supply.b sp, spectrographic; fer, ferron; aa, atomic absorption; chem, unspecified chemical; col, colorimetric; ssms, spark-source mass spectrometry;
grav, gravimetric; na, neutron activation; fs, flame spectrophotometry; alum, aluminon.c Approximate date of analysis.
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TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
Location8
ColoradoDenver
Connecticut
FloridaJacksonvilleMiamiSt. Petersburg
Water type
Hot springHot springWarm bicarbonate springMineral hot springMineral springMineral springMineral hot springHigh silica springGranite springs, ephemeralGranite springs, perennialVolcanic springs
RiverGulchArkansas RiverWell, arkoseThermal mineral springAcid mine waterSaline spring
Well, sandstoneWell, gneiss
WellWellWellRainwaterStreamLakeLake, phosphatic limestoneApalachicola RiverWell, limestoneCanals
PH
1.8
6.76.87.16.58.5
10.95.3-7.55.6-7.96.1-7.6
7-7.6
6.8-8.26.76.8
6.6
7.86.9
7.97.87.6
7-9.6
8
Al content(mgfl)
14310.40.61.60.10.230.90-0.120-0.190-0.25
0.023-0.1900.009-11.60.0025-0.0700.30.05-0.14290.24-1.2
0.10.1
0.0110.0120.0130-0.90-10-10-0.090.0730.10.00-1.8
Mean
(0.03)(0.018)(0.04)
(0.2-0.3)(0.2-0.3)(0.05)
Method15
fer
spsp
sp
aaaaaaaa
Datec
1953195619571957195719571957196419641964
1964-19651964-1965
1955195819331957
19551959
1967-19691967-19691967-1969
1971
19571968-1969
R<
186186186186186186186186189189189
184190190186186186186
186186
184184184191191191192185186193
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TABLE 11 (continued)
Aluminum Content of Lakes, Riven, and Subsuiface Wateis of North America
Ij?
Location3
GeorgiaAtlantaSavannah
HawaiiHonolulu
Water type
Chatahoochie RiverRiver
Well
Idaho
IllinoisChicago
IndianaFort Wayne
Iowa
KentuckyLouisville
Spring, quartz monzoniteWell, basaltHot mineral spring
Lake MichiganDeep-well brine
River
Well, sand
Ohio RiverRiverRiverWellWellAuger holeCoal-test holeStreamCane BranchMine waterWell, sandstoneSpring, shaleSpring, limestoneWell, sandstone brine
PH
6.66.6
6.6-7
7.57.79.1
7.87.2
7.6
7.4
7.34.9-5.23.5-7.7
5.17
2.4-7.53.8-6.15.2-7.22.5-7
2.55-67.24.98.27.3
Al content(mg/1)
0.1300.110
0.055-0.079
0.10.050.1
0.072
0.180
0.8
0.3900.5-10.1-210-0.31024-25
0-0.20.1-850.4-260.11.50.18.6
Mean Methodb Datec
(0.1)
(22)(11)
Ref.
184184
184
chemchem
195419561953
1955
1964-19651964-19651958-19591958-19591958-19591958-19591956-19581956-19591958-1959
195519551955
186186186
186186
184
186
184194194195195195195195194, 195195186186186
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TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
Location3
LouisianaNew OrleansShreveport
Maine
MarylandBaltimore
MichiganDetroit .FlintGrand Rapids
Water type
Mississippi RiverLakeMississippi RiverOil field waterOil field water
Shallow pond
ReservoirRiverPatuxent RiverSusquehanna RiverWell, graniteWell, gabbroWell, serpentineWell, gneissWell, marble
Detroit RiverFlint RiverLake MichiganLake Michigan tributariesLake Michigan offshoreSt Mary's RiverWell, sandstoneCopper mine water
PH
6.86.6
6.66.3
5.5-6.6
76.3
5.8-7.6
6.65.68.36.97.6
7.67.47.8
7.66.5
Al content(mg/1)
0.7100.0461.0105.03.1
0.024-0.489
0.0990.10.019-0.6200.0270.90.30.20.20.3 •
0.4100.6900.0770.010-1.5000.4000.002-0.0100.25.4
Mean
(0.190)
(0.353)
(0.006)
Methodb
col
sp
ssmsssmssp
Datec
195919581958
1969-1971
19651963-1965
195819511952195419531953
19721972196719561956
Re
184184185186186
196
184194197185186186186186186
184184184174174198186186
ca
VO
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00
I
3
Location3
MinnesotaMinneapolisSt. Paul
Mississippi
MissouriKansas City
Montana
Nebraska
Nevada
TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
Water type
New Hampshire
Mississippi RiverMississippi RiverMississippi RiverRiverLakeRiverWell, gravel
Well, clay
Missouri RiverStrip mine lakeStrip mine lakeStrip mine lakeCreekCreek
Spring, limestonePhosphate mine waterSaline ground water
Platte RiverReservoirWell, sandstoneWell, siltstone
Spring, perennialHot springSilver mine waterComstock Lode mine waterSilver mine water
Stream
PH
7.57.5
6.8-8.26.9-8.36.9-7.36.7-7.4
7.5
Alcontent(mg/1)
0.0880.0550.1-1.90.1-2.90.2-0.60.1-1.30.1
6.1
7.82.3-4.1
3-3.45.6-7.46.8-7.6
3-5.7
7.87.4
Acid
7.2-7.87.57.87.7
6.9-7.97.9
AcidAcid
Mean Methodb Date0
0.2
0.170-2.400102-4900.5-1710.001-0.0780.2-2.214-76
0.20.184
0.1-0.20.20.10.4
0-0.030.50.790003
0.2-0.6
1955
Ref.
chemchemchemchem
1964-19651964-19651964-19651964-1965
1955
184184199199199194186
186
gravgravgrav
1963-19661963-19661963-1966
19641964-1965
195619571933
1963196319541955
19641949
1965-1967
184200200200201199
186186186
199199186186
189186186186186
202
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TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
Location8
New Jersey
New Mexico
New YorkAlbanyBuffalo
North CarolinaCharlotte
North Dakota
Ohio
Water type
Surface watersBrookRaritan RiverRiverStreamPassaic RiverMcDonalds BrookSchuylkill RiverRamapo River
Spring, rhyoliteSulfur springThermal springSalt mine waterBrine seep
ReservoirLake ErieSt. Lawrence RiverNaCl-CaCl, springHudson River
Catawba RiverWell, andesiteWell, shaleWell, sandstone-gravel-
limestone
CreekWell, shaleWell, lignite
Maumee RiverCuyahoga River
PH
4.2-4.63.8-4.7
7.2 .1.97.25.2 •6.9
7.18
6.2
7.27.28.1
7.2-7.5
7-7.66.37.1
Alcontent(mgfl)
0.08-0.330.07-0.100.019-0.6000.038-0.570?-1.4000.021-0.6300.1-0.40.4-4.20.096-0.280
0.1560.3572.4
0.0170.0410.005-0.1503.40.304
0.0590.20.10.19-0.5
0.6-1.72.20.1
0.25-0.1380.018-0.038
Mean
(0.064)(0.027)
Methodb
aaaaspspsp
sp
chem
spsp
Datec
19681968
1963-19641963-1964
19701963-19641963-19641963-19641963-1964
19541949
19571958
1963-196419381958
19551955.
1968-1972
1964-196519541957
1963-19641963-1964
Re
203203204204205204204204204
186186186186186
184184198186
184186186206
199186186
198198
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§TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
1I
Location3
OklahomaOklahoma CityTulsa
Oregon
Pennsylvania
South Carolina
South Dakota
TennesseeChattanoogaNashville
Water type
Ohio RiverSpring, dolomiteMaumee River basin
LakeRiver
Santiam River ground waterNaCl-CaCl, spring
West Branch, Susquehanna RiverSchuylkill RiverRiverAcid mine streamMonongahela RiverAllegheny RiverOhio RiverRiver
Well, granite
Well, limestoneWell, quartziteGold mine drill holeBois de Sioux River
Tennessee RiverCumberland RiverRiverRiverCumberland River
PH
7.4
7.8
6.8-8.27.6
3.4-3.63.7-4.13.8-4.3
4-7
7
7.47.47.6
7.3r7.6
87.6
5.1-6.87.4-7.9
7.5
Al content(mg/D
0.2<0.012-5.320
0.1300.330
0.001-0.0190.12
3.9-113.8-4.80.2-4.540-33750.013-1.4300.06-3.2
0.1
0.10.20.350.2-0.8
0.2900.3100.1-10-0.20-0.2
Mean
(10)
(0.010)
(1.3)(1.3)
Method15
sp
aa
spspchem
chemchemchem
Date0
1963-19641955
1971-1973
1960-19681957
196119611961196519651965
1945-19461949-1950
1954
1954195419571963
196519651965
Ref.
198186207
184184
208186
204204204198198, 209194185185
186
186186186199
184184194194194
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TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
o
Locationa
TexasHoustonLubbock
UtahSalt Lake City
Virginia
WashingtonSeattle
West Virginia
WisconsinMilwaukee
Wyoming
Water type
San Jacinto RiverWellWell, sandstone
ReservoirBrine springNaCl-CaCl, spring
Roanoke River
RiverColumbia RiverSpring, schist-slate
Mine drainageCreekRiverRiverStreamSouth Branch, Potomac River
Lake MichiganWell, dolomite
Oil field water- Oil field waterGeyserHot springBig Sulfur PoolHot springHot spring, travertineYellowstone thermalsprings
pH
6.277.6
7.86.77.3
7.4
7.7
3.17-3.73.5
3.2-3.66.0-8.93.4-4.2
7.4
87.5
8.37.69.62.47
Acid1.97
6.2-6.61.9-9.8
Alcontent(mg/1)
0.3800.0320.1
0.0801.050.46
0.165-2.23
0.0070.2380.1
107-1873.3-126.2-6.30-1.116-180.1
0.0380.2
1.40.640.21.51462.40.2-0.4<0.1-51
Mean Methodb Datec
1955
19581958
1970
Ref.
184184186
184186186
176
aachemchemchemchemchem
col
19601960
196719651965196519651965
1954
1959195819571954
19541957
1960-1965
184185186
210194194194194204
184186
186186186186186186186211
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s
8Location11
Ontario
Quebec
British Columbia
Northwest Territory
Manitoba
MexicoSonoraYucatan
Water tyj
Rain waterSnow
St. Lawrence River
Fraser River
Slave RiverMackenzie River
Nelson RiverChurchill River
Copper mine waterLagoon
TABLE 11 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of North America
PH
Acid
Al content(mg/1)
0.5-1.120.07-1.00
0.276
0.526
11.41
0.0890.103
2220.0
Mean
(0.80)(0.46)
Methodb
fsfs
Date0
1965-19661965-1966
1958
1960
19461958
19601960
19331960
R(
to t
oH
—
t—»
to t
o
185
185
185185
185185
186185
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intent of Lakes, 1
Water type
RiverOil field waterVolcanic lakeLakeGround waterLagoonGround waterGround water
TABLE
Rivers, and
pH
5.8
12
Subsurface Waters of South America
Al content(mg/1)
0.26-316
1621.50.24.71.560.02
Datea
1878-1883193819301944
195719521956
Ref.
185186186185186185186186
Location
Argentina
Brazil
Peru
aApproximate date of analysis.
TABLE 13
Aluminum Content of Lakes, Rivers, and Subsurface Waters of Africa
Al contentLocation Water type pH (mg/1) Method Dateb Ref.
0.036-3.6 spa
8.95 1 sp0.0070.03-0.220.0240.1-1.52.20.2-0.4
13 1927 186
South Africa
Uganda
North RhodesiaMozambiqueLake TanganyikaTunisia
a Spectrographic.
RiverNaCl-CaClj springLakeSwampsRiverLakesRiverLakeNaCl-CaClj spring
b Approximate date of analysis.
1962
1938
1939
213186185185185185185185
June 1977 203
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Location
Austria
BulgariaFrance
Germany-
GreeceHungary
Iceland
RomaniaSwitzerlandUnited Kingdom
TABLE 14
Aluminum Content of Lakes, Rivers, and Subsurface Waters of Europe
Water type
LakeBitter springSaline ground waterGround waterRiverRiverRiverLakeNaCl-CaCIj hot springGas field water, hotBicarbonate wellMineral water wellLake Balaton shoreLake Balaton offshoreGround waterWellSurface waterIntermittent geyserErupting wellHot springMineralRiverRiverReservoir
PH
7.68
9.76.78.76.8
Al content(mg/1)
0.251.50.02-5.5
0.055-0.0700.24-3.6
4.40.50-0.86
0.830.24.20.34.80.026-0.0330.012-0.021
0-1.30-0.30-1.0
0.890.660.550.001181.90.039-0.0860.024
Mean
(0.02)(0.02)(0.04)
Methoda
sp
alumalum
spsp
Dateb
18981953196519681848193518931924193719511937
19571957
195019501950
184819721972
Ref.
185214215216185185185185186186186186217217218218218186186186219185220220
a sp, spectrographic; alum, aluminon.b Approximate date of analysis.
204 CRC Critical Reviews in Environmental Control
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TABLE 15
Aluminum Content of Lakes, Rivers, and Subsurface Waters of Asia
(Except U.S.S.R. and Oceania)
Location
Japan
Taiwan
VietnamIndonesia
Philippines
New Zealand
Water type
Lake surfaceLake, 5-12 mNaCl-CaCl, hot springLake, active volcanoVolcanic springVolcanic springActive volcanic springVolcanic springThermal springNaCl-CaClj springNaCl-CaCl, springThermal bicarbonate sulfate
springBicarbonate springHot springsLakeWell
Thermal springThermal springLakeVolcanic crater lakeHot springRiver from active crater
Active crater lake
Eight lakesNaCl-CaClj springGeyserVolcanic spring
PH
5.80.4
3.21.52.49.48.27.7
7.56.62.2-7.3
1.6Acid
Strong acid2.252.01
Strong acid
87.43.1
Alcontent(mg/1)
0.11-1.200.44-8.10713401313851070.20.30.9
1770.1-25.80.00690-0.008920.00212-0.00372
6001040.8-1.1413066222.6
7600
1.2-3.615.74
Mean Method3 Date" Ref.
alumalum
•
nana
19531953195519541951195519551941195419541949
1953
197019731973
1955
1941
1907
1922
1937
221221186186186186186186186186186
186
222175175
186186185186186223
186
186
186
a alum, aluminon; na, neutron activation;col, colorimetric.b Approximate date of analysis.
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3o
I
Table 15 (continued)
Aluminum Content of Lakes, Rivers, and Subsurface Waters of Asia
(Except U.S.S.R.)
ontentMeanLocation
AustraliaTasmania
Water type
Spring in active craterFumaroleThermal bicarbonate sulfate
drill holeHot bicarbonate springDrill hole
RiverCreek
PH
Strong acid2.86.7
8.37.3-8.3
Al content(mg/1)
18808.912
0.80.023-0.062
0.550.84
Methoda Date0
(0.05) col
Ref.
195919531955
19381967
19351935
186186186
186224
185185
Turkey NaCl-CaCl, hot spring 6.2 3.2 1948 186
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Location
EstoniaLithuaniaWhite RussiaMoldaviaDagestanSiberiaAzerbaijan
Kamchatka
Kuril Island
Volga River Basin
Unlocated
a sp, spectrographic.k Approximate date
TABLE 16
Aluminum Content of Lakes, Rivers, and Su
Water type
Wells, lakes, drill holesRiverRiverMineral waterGeothermal wellNaCl-CaCl, warm springMineral watersOil field waterGeyserBoiling mud potHot crater lakeVolcanic springMud potVolga RiverReservoirSoil watersForest soil waterPodzolic subsoil waterMine water
of analysis.
pH
8.15
8.41.86Strong acid1.71.7
4.75
bsurface Waters of t
Al content(mg/1)
0.46-1.770.0015-0.13360.0091-0.0143.023.49-24.159.30.593-0.39590.3-80.8
4446293780.001->10.0008-0.0260.26-0.290-0.0410.5-2.5
144.0 (max.)
Method
sp"
Date0
sp
sp
Ref.
196519691965
11969193719681960194919371958195819581963196719711965
225226227228229186230231186186186186186232233234235236237
the data of Tables 11 to 17 will not have beencollected using these techniques. As a general rule,all aluminum values reported before 1940 shouldbe regarded with skepticism. Even with thesecaveats, the following verities can be extractedfrom the data:
1. Acid waters consistently contain muchmore soluble aluminum than neutral or alkalinewaters.
2. Highly saline waters contain higher levelsof aluminum than fresh waters.
3. Hot waters tend to contain more alumi-num than cold waters.
4. Moving waters give higher aluminumanalyses than quiescent waters.
There are many different kinds of acid waters,although acid mine drainage has received the mosta t ten t ion . 1 9 5 ' 2 0 0 ' 2 1 0 ' 2 5 2 ' 2 5 3 The process bywhich acid is formed is probably not relevant tothe release of aluminum, but it is well establishedthat pyrite (FeS2) exposed to weathering eitherthrough opening of a coal seam or by removal ofthe overburden is oxidized both chemically andmicrobiologically to sulfuric acid. One would
anticipate that alkaline waters with pH levelsgreater than 9 would also contain more aluminum;that they do not is a further demonstration of thelimited solubility of aged aluminum-bearingformations as compared to freshly precipitatedaluminum hydroxide. Hem254 has discussed thesources of aluminum in natural waters.
The increased solubility of aluminum in saltwells and springs may be due to complexing of thealuminum cation by anions such as sulfate; it mayalso be due, in part, to the strongly depressingeffect solutions of high ionic strength have on theactivity coefficients of polyvalent ions. Becausesolubility equilibria are based on activities ratherthan concentrations, a brine solution canaccommodate more aluminum at equilibrium thanfresh water. This raises the question of whysoluble aluminum is apparently less prevalent insea water than in fresh water. One possible answeris that colloidal aluminum particles are consoli-dated in seawater, so that material too fine to beremoved by filtration is greatly reduced in theoceans.
The higher apparent solubility of aluminum inmoving waters than in quiescent waters suggeststhat much of what is alleged to be soluble
June 1977 207
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Location
Pacific BasinPacific Ocean, Japan
Inland Sea, Japan
Japan SeaPuget Sound, WashingtonSan Juan Channel, WashingtonWashington-British Columbia coastCalifornia coast
Gulf of Mexico
Atlantic regionU.S.-Canada coastNew York Bight, surfaceNortheast Atlantic
English ChannelAegean Sea (caldera)Black SeaIndian Ocean
Weddell Sea, AntarcticaUnspecified
TABLE 17
Prevalence of Aluminum in Seawatei
Al form
SolubleUnknownUnknownUnknownUnknownSolubleSolubleParticulateTotal (?)SolubleParticulateSolubleSolubleParticulate
SolubleParticulateParticulateParticulateParticulateUnknownUnknownSolubleSolubleSolubleUnknownUnknown
Al content(mg/1)
0.00664-0.008260.2880.0090.295-0.3250.315-0.3600.005-0.0070.007-0.0150.002-0.1540.580.002-0.0070.0002-0.00800.0037-0.1660.002-0.0100.0002-0.0102
0.002-0.0070.0014-0.1300.0093-0.12050.0006-0.0660.01-0.950.006-0.0070.01020.02680.0368-1.1200.001
Mean
(0.011)
(0.0098)
(0.002)
(1.9)(0.008)
Methoda
napolpolalumalumflcolferspflflspflfl
flnafercolgrav
colcolfl
Date5
19721952195219521952196119391963195419611961195919531971
1953197219681952
1948-19491967196719621964196119321966
Ref.
185238238239239154240241167154154154153155
153242243244245246247248249154250251
a na, neutron activation; pol, polarographic; alum, aluminon; fl, fluorimetric; col, colorimetric; sp, spectrographic; fer,ferron; grav, gravimetric.
b Approximate date of analysis.
aluminum is suspended material; however, thehigher levels may also be due to aluminum-complexing organics present in many rivers andstreams.
Thus far, only chemical equilibria have beenconsidered, but equilibria involving bioaccumula-tion of aluminum may also influence levels ofdissolved aluminum in water. Relatively little workhas been carried out in this area, although it isknown that aluminum is ubiquitous at the tracelevel in most tissues of almost every organism.1
Silvey188 has found that Lemna minor (duck-
weed), a floating aquatic plant of the AmericanRiver in California, contains 1,980 mg/kg ofaluminum, corresponding to a concentrationfactor of 660,000. A common brown alga off theCalifornia coast contains 14.3 mg/kg, for aconcentration factor of 1500. A quantitativeevaluation of the significance of bioaccumulationmust await a systematic study of the uptake ofaluminum by the flora and microflora of the sea.Among terrestrial plants, the lycopodia are themost prodigious accumulators of aluminum, withlevels occasionally exceeding 4 g/kg of livingplant.2 s s
208 CRC Critical Reviews in Environmental Control
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REFERENCES
1. Sorenson, J. R. J., Campbell, I. R., Tepper, L. B., and Lingg, R. D., Aluminum in the environment and humanhealth, Environ. Health Perspect., 8, 3, 1974.
2. Sprague, J. B., "The ABC's of pollutant bioassay using fish", in Biological Methods for the Assessment of WaterQuality, Cairns, J., Jr. and Dickson, K. L., Ed., Spec. Tech. Publ. 528, American Society for Testing and Materials,Philadelphia, 1973, 6.
3. Thomas, A., Effects of certain metallic salts upon fishes, Trans. Am. Fish. Soc., 44, 121, 1915.4. Sanborn, N. H., The lethal effect of certain chemicals on fresh water fish, Canner. 101(5), 13, 1945.5. Minkina, A. L., On the action of iron and aluminum on fish, Trudy Mosk. Zooparka, 3, 23, 1946; as quoted by
Doudoroff, P. and Katz, M., Critical review of literature on the toxicity of industrial wastes and their components tofish. II. Metals, as salts, Sewage Ind. Wastes, 25, 802, 1953.
6. Penny, C. and Adams, C., 4th Report, Royal Commission on Pollution of Rivers in Scotland, Vol. 2, Evidence,London, 1863, 377; as quoted by Ellis, M. M., Dectection and measurement of stream pollution, Bull. U.S. Bur.Fish., 48(22), 365, 1937.
7. Ellis, M. M., Detection and measurement of stream pollution, Bull. U.S. Bur. Fish., 48(22), 365, 1937.8. McGuigan, H. A., The pharmacology of iron and aluminum in relation to therapeutic uses, J. Lab. Clin. Med., 12,
790, 1927.9. Teulon, F. and Simeon, C., Toxicological Tests of Chemical Products on Freshwater Fish, Rapport CEA-R2938,
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