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Chern. Anal.

(Warsaw), 44, 1 (1999)


AluDliniuIDSpeciation in Natural Waters
by Krystyna Pyrzynskal,Ewa and Adam Hulanicki
1
University ofWarsaw,. Pasteura 1,02-093 Warsaw, Poland
2Uludag University, Faculty ofScience andArts, Department of Chemistry, 16058 Bursa, Turkey
Key words: aluminium speciation analysis, analytical methods, reviews
Thepresence<ofaluminiumin the form of different species in natural waters receives
anincreasing attention due to better understanding of its bioavailability, toxicity and
transport mechanism.. Recently a number of nlethods for fractionating of alulninium
have been developed. Most of them are operationally defined, since the validation of
what is really measured in real smnples is very difficult. This review concerns the
specific problems of aluminium speciation analysis. and highlights some important
methods used for this purpose.
Badania dotyczqce toksycznosci, biodostvpnosci i obiegu gUnu w srodowisku natural-
nymSq zwiqzane z wystvpowaniem tego metalu w postaci r6znych zwiqzk6w w wodach
naturalnych. W ostatnich latach w literaturze ukazalo si
v
wieleprac opisujqcych r6zne
metody badania specjacji glinu. Celemniniejszej pracyjest przedstawienie najwazniej-
szych aspekt6w zwiqzanychzbadaniem specjacji glinu oraz krytyczne przedstawienie
opisanych w literaturze metod analitycznych.
The chemistry of aluminium and itsspeciation becomes an area of intensive study
in recent years [1,2]. Due to limited solubility in the absence of complexing ligands
atthe pH normally encountered in most natural waters,alurninium content is low;
the average concentration or10 Jlg 1-1 for the hydrosphere [3,4]and of 100-500 flg 1-1
for fresh water [5-7] has been reported. High concentration such as 1.6 mg 1-1 of Al
in surface water from the Lysina catechumens in the Czech Republic has also been
determined [8]. The present great interest in the aquatic chemistry of aluminium
originates, to a large extent, froin input of acids into the envirpnrnent, mainly through
fossil fuels containing sulfur or nitrogen. This leads to a decrease of pH in waters
and soils with poorly buffered bedrocks, and cause a greater mobility of aluminium
in the environment. Aluminium solubilised by ,acids is toxic to plants because it
antagonises calcium' binding essential for root cell surfaces [9]. The presence of some
labile aluminium species in surface waters is also toxic to fish [10].
2
K. Pyrzynska et al.
In clinical chemistry this metal is well known for its toxicity to uraemia patients
[11]. Aluminium transfer through the dialysis membrane to the blood and its accu-
mulation in bone and brain tis'sue have been associated with a series of clinical
disorders suffered by the patients undergoing regular haemodialysis [12]. The etio-
logic role of aluminium in Alzheimers disease and other neurodegenerative diseases
is still controversial [13].
The role of aluminium in complex ecosystems or living organisms, its tox-
icity, reacti vity or bioavailability dependsmainly on its chemical form. Therefore
the chemical bonds in which it is involved and eventual association with other
components of given sample matrix are of a great importance. In aqueous solu-
tions aluminium exists in a number of complexes, all of which are in dynamic
equilibrium. Each species can also undergo several changes in a respect chain:
A1
3
+ +-+
AOH)3' then, with an increase in pH, the anionic fonns can appear [14]. Beside the
importance of pH, the distribution of aluminium species is depending also on the total metal
concentration, temperature and the presence of different inorganic and organic .ligands
[15,16]. The A1
3
+, AIOH
2
+ and Al(OR)! species are more reactive and toxic than
polymeric forms and organically bound alumin,ium [17]. The main inorganic ligand,
apart from hydroxide is fluoride, which forms very strong complexes with A1
3
+. Since
fluoride concentration in natural waters is generally lower than that of aluminium,
mainly Alp2+ and AIF
2
+ are present. The presence of fluoride ions can reduce the
toxicity of Al to fish and, as it was reported [18], reduces the incidence of dialysis
dementia syndrome. It was found that aluminium sulfato, phosphato and silicate
complexes also exist in natural waters. Recent studies have shown that the toxic effect
of Al in natural waters is diminished in the presence of silica acid, as insoluble
hydroxoaluminosilicates are formed [19,20]. Most organic compounds with hydro-
xylic and carboxylic groups could form stable complexes with aluminium. The
organic ligands may be mainly humic and fulvic acids, since these constitute.a major
part of the dissolved organic material in natural waters [21,22].
In the recent years various analytical methods for speciation of aluminium in
waters were presented in the literature. In many cases they are based on similar
procedures (Table 1). We have no intention to present all the methods. The aim of
this review was rather to cover general aspects .of aluminium speciation and to
highlight the most important ideas.
Table 1. Fractionaction of aqueous aluminium
Smnple treatment Aluminiumfraction Fraction composition
Acid digestion Total reactive (Al
t
) Acid soluble fonns
Without digestion Total monomeric Inorganic and organic
(AIm) monomeric complexes
Alt-Al
m
Colloidal, polymeric and
Acid soluble strong organic complexes
Cation-exchange
treatment
Alulniniunt speciation
Non-labile monomeric
Alm-Al
o
Labile monomeric
Monomeric organic
complexes
AI
3
+, hydroxide, sulfate
fluoride complexes
3
SAMPLING AND STORAGE
In the case of speciation analysis, which is in the case of aluInini urn the oper-
ationally defined fractionation study, sample handling is of great importance since
any treatment Of natural sample might change tpedistribution of AI. among different
species. Stor.age may also affect the chemistry of samples that werenotin equilibrium
at the time of collection and when the samples are stored at a.temperaturewhich
differsgreatly.from their sampling [161.
The experiments, carried out, by ;Fairman elal. [1,7]. haye shown"that 'aluminium
concentratipn at the ,level below 50 Jlg 1-1 was stablein high density polyethylene
container where 0.1 mol 1-1 nitric .or citric acids tllese conditions
lake and tap water samples were stable up to 30 .days. The losses of metal, which
were later observed, could be ,explained by the precipitation of polymeric hydro-
xoaluminium species 1:>Y the container,material.
" On,e of the most controversial with aluminiumspeeiation
is the sample. filtration.. It is; possible . that the distribution of aluminium
species could change upon filtration._ Many analytical methC).ds require prefiltered
samples (usually through 0.45 JIm filter) togive repeatable results. How,ever" alumi-
ni urn adsorbed s,olids (clays, or colloidal particles of humic and fulvic
substC;lnces) is relativelylabile and could account for a considera"ble part of inorganic
monomeric aluminium. fraction measured in \vC;ltet samples [231. Tbe content of this
fraction decreased With, higher and small filter pore size used.
METHODS OF ALUMINIUM' SPECIATION
The determination of .individual alYllliniumspecies in natural waters is very
difficult due to thdrBarticipation in. dynamic reactions, their low concentration.and
t4e presence of complex matrix, mostly of that might interfere with
the analytical methods applied for the determination. <The. fraction of particular
concern, usually called as, free AI, comprisesAI
3
+, AIOH
2
+, AI(OH)i andalu,minium
in very labile complexes (mainly inorgani9).Organically alumi-
nium appear to be muchiess toxic than inorganic forms, particularly. for plants and
fish.
Two different types of procedures are used for aluminium speciation. The
theoretical approach involves the use of thermodynamic data together with analyti-
4 K. Pyrzynska et al.
cally determined content of total aluminium and the significant ligands. The ex-
perimental approach involves the analytical separation of various Al species based
on different reaction kinetics with complexing reagent and/or the separation based
on size or charge of determined species.
Theoretical approach
As the sampling of the natural analytes is often associated with a change in their
environmental, this can disturbs the existing equilibrium and cause a large uncer-
tainty of the obtained results. At the present state of computer science, with available
powerful computers and data bases of physicochemical constants, it may be a rational
way to make a computational approach. The concentration of different forms.of
aluminium that are present in -a sample could be calculated from the analytically
determined content of total aluminium and--the significant ligands followed by the
calculation based on the available equilibrium constants. Some examples ofstich an
approach for Al have been already published [24-28].
Most of the theoretical models describe only inorgani'c monomeric aluminium
species without considering polymeric and organic forms. Even when -the authors
deal with the AI-organic complexes, they choose different ligands, so it is difficult
to compare their results [24-26]. In some models the equilibrium reactions with iron
and manganese s.pecies are. not included, although aluminium complexation to
hydrous particle surfaces has been demonstrated [29,30]. Another problem concerns
the validity and completeness of the thermodynamic data base on which this approach
fully depends. Much of the unidentified organic carbon exists as a poorly charac-
terised humic material [31]. Discrepancies between analytically measured and cal-
culated values arise from model inadequacy as well as analytical errors.
Bertsch and Anderson [28] compared the distribution of aluminium between
uncomplexed and oxalato and citrato species determined by ion chromatography and
calculated utilising thermodynamic constants. Good agreement was obtained -- for
different ratios of oxalate ions to metal. However, the citrato complexes were
extremely sensitive to changes in ionic strength and significant redistribution of
aluminium species was observed. The measured fraction of citrato complexed alumi-
nium was lower at the cost of free metal in comparison with the calculated data.
The calculations based on the thermodynamic __ data, working well in model
systems, fail in water samples because they do not take into account aluminium
associated with particulate matter. The equilibrium with large organic ligands (humic
acids) and aluminium-silicate systems are not know sufficiently well. This as well as
the slow kinetics of several processes may introduce undefined errors. The measure-
ments with fluoride ion-selective electrode also did not give concluding results
~ c u s e of other ligands competing to aluminium [32].
In conclusion the computation approach may give only fractional information but
cannot solve the problem in a more general way. In natural water, often there is no
equilibrium, in particular in the case of heterogeneous processes.
Aluminiumspeciation
Analytical speciation
5
The .experinlental approach in speciation .of aluminium involves the separation
of. various Al forms based mainly on differential reaction kinetics. with. organic
complexing .. reagents, non-chromatographic separation of inorganic species from
organic-bound and colloidal aluminium on solid sorbents and hyphenated chromato-
graphic or electrophoretic methods. However, no specific and direct method for
separation and determination of individual aluminium species exists. Only a number
of fractional procedures have been developed to distinguish the groups ofAl species.
These procedures usually measure operationally defined metal fractions, which not
always coincident and thus makes. a direct comparison of the published methods
difficult. Although atotal characterisation of aluminium distribution is desired, from
environmental point of view, the most important fraction consists.of the morereactive
monomeric inorganic species. .
Spectrophotometric and fluorimetric reagents. One of the most frequently
used metpods has been based .its
metallochromic reagents followed by spectrophotolnetric or fluorilnetricanalysis.
Short reaction times (2-60s) and
the. Inorestable polymeric complexes..To. minimise' interferences, .mainly from
Fe(III), hydroxylamine and 1,10-phenantr()line are used as a masking agent. The
presence of humic. substances. in natural. waters can. also cause interferences, espe-
cially in UV or lower visible region. detection..This problem is usually overcome by
extraction of the forlned complex into an organic solvent, which also allows to
preconcentrate the analyte and gives a possibility of storing the extract for the
analysis.
8-hydroxyquinoline (oxine) has been often applied to measure the.most quickly
reacting forms of aluminium [245,32-36]. The principle of this method, introduced
by Okura et al. [33], is based on the complexation of monomeric Alspecies with
oxine at a chosen pH and the rapid extraction of the formed water insoluble complex
into chloroform. The concentration of these species is determined in the organic phase
spectrophotoluetrically at 390-420 nm or by flame atomic absorption spectrometry.
Another spectrophotometric reagent that has been used is ferron [37-42]. The
complex of aluminium with ferron absorbs light at approximately 370 nm and it is,.
as opposite to oxine complex, fairly soluble in water.. The fraction of aluminium,
which reacts almost immediately with ferron, was considered to consist of simple
monomeric species. The second fraction, reacting more slowly, was considered to
represent polynuclear species, while the third one was supposed to represent small
solid particles. Jardine and Zelazny [40] found that sulphate and fulvate complexes
react with ferron identically to uncomplexed monomeric aluminium. From the other
hand, it was also reported that aluminium complexed with fulvic acid reacts slowly
with ferron [41], while fluorocomplexes react partially for reaction times between
15s and 30 min [41]. The ferron method could be a subject to interferences from other
metal ions, especially manganese.
The colour development of aluminium with Pyrocatechol Violet (peV) has been
widely used for determination of the content of inorganic monomeric Al [5,23,43-
6
K. Pyrzynska et al.
Separator
Extraction
coil (3m)
Pump
mllmin
Buffer
Oxine ----+o-L-:=:-..........---.,...,..
Water
---+-"---"-+0--......
47]. An advantage of PCV method compared with earlier mentioned spectrophotome-
tric reagents, is that its aluminium complex absorbs light at higher wavelength (580 nm)
which makes it less sensitive to interferences from humic substances. Silicon can also
affect measurements in silicate-rich water [23]. . '0',
The 8-hydroxyquinoline-5-sulfonic acid(8-HQS) forms watersoluble complexes
with aluminium and has been mostly' used as fluorimetric reagent [48-50]. in the
presence of cationic surfactants (e.g. cetyltrimethylammonium bromide) lO-fold an
increase in the fluorescence intensity was observed [4,8].
The laborious operations of the sample pretreatment andthe spectrophotometric
measurement can be substantially simplified by usingthe methodologies of flo'Y-in-
jection analysis (PIA). There are some obvious advantages with this approach, such
as ease of operation, a better control and repeatability of the reaction time, which
makes it possible to use a very short reaction time, an increased sample throughput
and a possibility of mechanisation. Also of very great importance is ateduced human
IJU-J., .....I.'-'.A.IJ ..." ... .I.'-".I..1. in' time-consuming operations such as sample reagent
1'Y\1J.i1""\lr\nl':1ltlr\n and calibration of measuring_system [5'1,52]. Several FIA proceures
have been reported for fractionation of aluminium species using oxine [8,25] orpeV
'[5,41-46] as the' cornplexing reagents. A schematic diagram of the' flow-injection
set-up used by Clarket ai. [81 for aluminium is shown in Figure 1. After
addition and 1,IO-phenantroline for decreasing
ces, species react within 2.3 s oxine at pH 5.0 (acetate buffer). The
formed complex is then extracted at thesame pH value and measured at 390 nm.This
method, according to the authors, ,allows to determine the sum of A1
3
+, i.e. its
monomeric hydroxo species and sulfato, silicato and carbonato .. The
complexes with citrate, humic or fulvic acids and Alp2+ are not included'
"quickly reacting" aluminium fraction. '
Sample

Chloroform
Figure 1. Schematic diagram' of the FIA system used for the speciation of aluminium (adopted from [8]
with kind permission of Elsevier Science-NL
Hawke and Powell' [45] compared the chromophores - pyrocatechol violet,
chrome azurol S (CAS) and eriochrome cyanin'R (ECR) for estimatiqn of kinetically
labile fraction, of aluminium using FIA 1;hei1
4
; results showed that _PCV
rather fast. The percentage of aluminium reaGted in lOs were 45% for CAS, 48% for
ECR and 90% for pev. They observed some changes in A
max
for Al-chromophore
Aluminium speciation 7
complexes and the formation ofan isobestic point at A> Amax.It indicated a sequence
of reactions within the first 10 s an intermediate species forms rapidly followed by
conversion to the. 1: 1 complex. Thus, the authors proposed monitoring absorbance at
the isobesticpoint,to estimate of kinetically labile ( lOs reaction) and equilibrium
reactive (10 min reaction) aluminium from a single injection.
Ion exchange methods. From the literature data it follows .that the most widely
used method is that proposed by Driscoll [53]. It is based on the separation of
inorganic monomeric Al from organic complexes'with a cation exchange column.
The organic species are predominantly of anionic character and are assumed not to
be adsorbed. In general, the Driscoll method offers a direct measurement of three
operationally defined fractions:(l) total reactive Al after acid digestion (AIr), (2)
total monomeric Al analysed in separate step without digestion and (Al
tm
) and (3)
non-labile monomeric AI(Al
n1
) determined,after passing asample through the column
packed with cation exchange resin Amberlite IRA-120.,The difference between the
two last measured values gives inorganic 'monomeric AI. This fraction, considered
to be the more toxic one, is thoughtto include A1
3
+ along withitshydroxo, sulfato,
fluoro and silicato complexes. Additiqnally "acid soluble AI" fr ac;tion can be ob-
tained by subtractingtotal reactive andtotaI'mono111eric aluminium. Driscoll proce-
dure is refereed asa classic by now and been often applied with various modification
[6,50,54-58]. However, re-equilibrium of the species in a sample can occur during
its passage through the ion exchange column and organic complexes can release
aluminium. It would result in an overestimation of inorganic monomeric fraction.
Observation indicate that the dissociation of organic aluminium, species is often
variable and depends on the ratio of aluminium to organic carbon [59,60]. In order
to avoid this the resil1,. has to be sodium chloride solution, which
must have the same conductivity as the; water samples for analysis. Thisis to ensure
that the sample pH does not change during analytical procedure. To shorten this
preparative step it is better to condition the resin to achieved its sodium form [17,50].
Chelex 100, the chelating cation exchange resin with iminodiactetate functional
groups, has .applied in aluminium speciation schemes to distinguish be-
tween resin (labile) and nonexchangeable aluminium species [61-65].
In such procedures the resin has to be very carefully preconditioned with a synthetic
solution containing a mixture of Ca
2
+, ". H,+with similar
to those .encountered in natural waters. Some authors suggested that the tendency of
the resin to shrink makes the batch technique more suitable arid allows a precise
control of the contact sample and resin [61,62] . However, . in the ,
method it is not possible to differentiate that it groups the monomeric inorganic and
organic labile complexes together with low molecular weight polYl11er,ic species [61].
Chakrabarti tt at. [63.,64] applied Chdex 100 resi.n 3:dditionally to filtrati 0rl, ultrafil-
tration and anodic stripping voltammetry, to determine the operationally defined
various aluminium fractions in rivet water, rain and snow. ,
Tqe analytical for determining .the speciation aluminium in acidic
freshwaters,presented in Fig. 2, included three major operations: filtration, ion
exchange and photooxiation[62]:Neither contamination nor analyte loss was ob-
served' with 0'.4' J.lin' filters. After UV irradiation the nonexchangeable fraction of
8 K. Pyrzynska et ai.
aluminium, which was not retained onChelex resin, practically disappeared. It
suggesting that the major portion of nonexchangeable AI initially present in the
samples was associated with organic matter. However, in many of the tested samples
appreciable losses of aluminium occurred during photolysis, presumably .due to
adsorption onto the walls of the quartz reaction vessels.
Acid-extractable
particulate Al
!

Chelex
aeid digestion

Nonexchangeable
filterable Al
FiltratioD
1

Totalfilterable
Al
Nonexchangeable
filterable Al
E =B - C Exchangeablefilterable fraction
F =C - D Nonexchangeable organicfilterable fraction
Figure 2. Fractionation scheme for speciation of aluminiuln (based on the procedure from [62])
An alternative approach to the speciation of aluminium is based on the selective
retention of metals (or its rapidly formed complexes) on a suitable adsorbent ina
microcolumn. Such a method after choosing an appropriate reagent and adsorbent
can be very selective and can also involve a preconcentration step. Thus, Fair,man et
al.[65]used'thehydrophobic sorbent packed in very small column
of a volume of 88 JlI to retain a complex formed in an initial 2-3 s time of reactiol,1
of aluminium and oxine in a flow-injection manifold. The method was adopted to
Aluminium speciation 9
the manual field.processing of.samples with subsequentelution of the adsorbed
complex with hydrochloric. acid in the laboratory. The oxine-derivatisedFractogel
(vinyl polymer gel) was also applied for preconcentration of aluminium species
[66,67]. The maximum retention ofaluminium.occursat pH 5. The elution can be
done bybackwashing with either 0.05 He} [66] or 0.02 mol 1-1 of NaOH via
therapidquantitativeconversiQn of AI(oxine}Jcomplex to AI(OH)4'
[67,68]. The AIF
2
+ and AIF
2
+ .species are. retained quantitatively and therefore
contribute to "free.Al".The . peak that follows.injections of
samples containing organic ligands represents moderately labile Al (Fig. 3b) [67]. This
is an aluminium fraction which is not sufficiently byretained by the oxine microcolumn.
The investigation ofpolymeric aluminium (e.g. Al1304(OH)24(H20 )I!) revealed that
the Al polymers maybe complexed by the oxinemicrocolumn but not eluted with
the free and very labile fraction ofAl [67] .. This fraction can be quantify usingforits
elution 0.2 mol 1-1 NaOH solution and 2 min stopped-flow.
0.6
a
Analyte elution
peak .(Ats;
(]) 0-.4
o
c
as
.c
a-
o 0.2
(/J
.c

o
Sample
injection
I
N.ollcolurIu)-
reactive AI
Blank elution
peaks
i
I
I
a
H
II
II
,II
II
"
. ,--_ ,--.. ,_.
" . . v . tI
I
Repeat...

15 10
Time, min
5
-O.2+------+----__- ..........---......jI--....----I
o
0.8
b
Analyte elution
p$ak (AjSn
0.6
CD
o
c:
as
.0
a-
o
U)
.0
<C.
0.4
0.2
o
Non column-
reactive AI
10 8 6 4
Blank elution
..... O.2.....__ ..... ......__......jI___-.....
o 2
Time, min
Figure 3. Detection of signals for (a) 5 x 10-
3
mol I-I of AP+ in standard solution and (b) in natural
samples after separation on oxine microcolumn (reprinted from [67] with kind permission of
Science - NL)
10
K. Pyrzynska et aL
Chromatographic and electrophoretic methods. High-performance 'liquid
chromatography (HPLC) is also a very useful technique in speciation analysis of
aluminium. Because of the ability to determine of individual species, this method
may provide the most probably information on aluminium species in aqueous systems
[28,48,49,69-71]. It can also separate fluoride species from the other inorganic
monomeric Al fraction, which is difficult with other described methods. However,
several problems occurred, including the inability to quantitatively detection of
stronger aluminium organic complexes at the.low concentration in surfacewater[69],
interferences from some metal ions including iron [48,69], poor chromatographic
separation of species using isocratic elution [46,47] and the dissociation of alumi-
nium complexes on the cation exchange column when pH and ionic strength of the
eluent and sample are not identical, which resulted ina poor agreement with the
thermodynamic calculations [28]. Also,a high concentration of organic matter could
affect the columns and reduce their useful life time.
An analysis of lake water samples (pH 5.31) by HPLC indicatf;d three peaks [70].
The first peak corresponds to the species with a charge less than or equal to +1 and
is assigned to organically bound aluminium. The species with a charge of +2
correspond to the second peak and represent Alp2+ and possibly other Al organic
Finally, the third peak represents A1
3
+and its soluble hydrolysis species.
The measurement of this sample indicated that a considerable amount of the total
monomeric alun1inium (65-70%) is organically bound.
An ion-pair chromatographic method was also evaluated for speciation of alumi-
nium at concentrations down to a, g JlI-
I
[70]. The stationary ph,ase of the column
consisted of a neutral,ul1polar polystyrene-divilylbenzene resin a large surface
area. Butane sulfonic acid Was used as: lipophilic ion added to the mobile phase
(NH
4
CI, pH=3.0). It was found that alu,minium fluoride and several five- or six-mem-
bered complexes (oxalato, citrato, tartrato, malonato) are sufficiently stable to be
determined. But their stability depends on pH of both the sample and the eluent and
on residence time on the chromatographic column.
Usually in HPLC aluminium determination fluorimetric detection has been done
with a post column reagent such as 8-HQS [48,49], pev [69] and lumogallion [70].
The lowest reported detection limits were 0.95 1-1 [48] andO.19 1-1 [70].
The reverse-phase chromatography was also,used for speciation of aJuminium in
the presence of humic acids [71]. The best separation was achieved on,RP-18HCD
column, when acetonitrile-water (85-1?% v/v) solution was used as an eluent.
Determination of aluminium in 0.2 ml fractions was performed by off-line GFAAS.
The results shows clearly (Fig. 4) that a part of the metal is eluted before the humic
acid peaks appear on the chromatogram. The biggest part is hoWever eluted together
with some components of humic acids dissolved in the sample.
Capillary electrophoresis (CZE)"was applied fot analysis of fluoro- and
oxalatoaluminium complexes present in aqueous solutions [72]. Detection was per-
formed using indirect absorption method with a background electrolyte containing
imidazole. The detection limit for uncqrnplexed Al and complexed
species was found to be about 10 nmol I-I. The, CZEmethod possessesa,distinct
advantage over HPLC for the separation of sample solutions containingfluoro and
Aluminium speciation 11
oxalatocomplexes. Using HPLC only uncomplexed Al species and AIF
2
+ produced
discrete chromatographic peaks while AIF! and monooxalatoaluminium species
co-eluted as a single peak under isocratic conditions [28].
-=
0.07
0.35
-=
0

0.06
0.30
.S
u "!-l
(I,) U
... Qj
Qj
0.05
en
"'t:S

0,04
0.20
en

<
0.03
0.15
2-

(I,)
0.02
0.10
c.J Qj
=
u
Cd
0,01
0.05
I::
"Q t't:I
I-i
..0
0
0.00
J-c
en
0.00 0
..c
V.1
<
,.Q
-0,01
-0.05 <
co lO
0 lO 0
0 0 ,...l
v-4 e-.i
Time,min
Figure 4e Chromatogram profile of humic acid with superimposed aluminium elution profiles determined
by GFAAS (represented by bars). Conditions: RP-18HCD column, isocratic elution \Vithacetoni-
trile-water (85-15% v\v) solution of 1 ml min-
1
flow rate, fraction volume 0.2 ml [71]
VALIDATION OF METHODS FOR ALUMINIUM SPECIATION STUDY
Operational speciation, to ",hich belongs the methods of
is generally difficult to be properly validated. The developed procedure are based. on
the relative inertness/lability of the species and result in a strong infJuence of
numerous experimental parameters, such as concentration of reagents used, the
presence and concentration of accompanying species, .time, temperature or mixing
conditions of reaction involved. Those parameters. are usually difficult to be stan-
dardised. Difficult to standardise is also kinetics of many reactions of aluminium in
solution, especially in the samples containing poorly defined organic matter. On the
other hand it is known, that some. reactions, as e.g. the monomeric - polymeric
exchange and the reaction involving pH changes,may be relatively rapid in labora-
tory and also in environment.
This,. at least partially, explains the lack of reliable certified reference material
for the study of aluminium speciation. The complexity of the system also restricts a
possibility of application of the recovery tests for validation of the method. Therefore
such validation must 'be based on the comparison of different procedures, and a
careful interpretation of all steps of the procedures and final results must be made.
Such a comparison has been carried out and, as a standard procedure the Driscoll
method with pyrocatechol violet detection of the aluminium fractions was accepted.
Those fractions correspond to (a) acid reactive aluminium (AIr), (b) tot&l monomeric
aluminium (Al
tm
) and (c) non-labile monomeric aluminium (Alnl).The dependence
on experimental condition is indicated by the necessity of keeping the exact times of
reactions. In this respect the use of FIA is of advantage, because of better reproduci-
bility of conditions and in consequence of results.
12 K. Pyrzynska et al.
In order to clarify the measurement of the aqueous aluminium species the
program named "The Standards. Measurements and Testing Programme" (formerly
BCR) initiated the interlaboratory study for the determination of "labile monomeric
AI" fraction [17]. The distributed samples originated from lake and tap waters and
after spiking with AI
3
+, the final aluminium concentrations ranged from 25 to 1000
Ilg 1-
1
(pH =5.2-7.0). The Driscoll method with pyrocatechol violet detection [50]
was used as a reference method by each laboratory and also an alternative method
developed in-house by each participant. Among them was the FIA system with the
fluorimetric detection using 8-HQS [50], HPLC method with a post-column derivati-
sation o l l o w ~ by the fluorescence detection [40] and the flow-injection Driscoll-
PCV method [73]. Generally, a good agreem.ent between the reference and
alternative methods was obtained for the samples with small additions of aluminium
[17]. The content of labile monomeric Al in test samples without any additional Al
spike was very close to the detection limit for frequently used Driscoll method. The
samples \vith the highest aluminium additions gave few useful data due to the
precipitation of aluminium. When evaluating these results, one must keep in mind
that speciation measurements in samples with such low levels of monomeric alumi-
ni urn fraction is very difficult.
From the practical points of view, it is most important to have a reliable procedure
for determination of toxic species, which are the AIOH
2
+ ions. However, there is no
definite proof that other species such as AI(OH)!, Al02" or even AICI
2
+ which
relatively rapidly change into AIOH
2
+should not be considered similarly as toxic. In
consequence two questions should be answered: (1) which species should bedefi-
nitely determined as toxic, and (2) how thedetetmination of operationally defined
species can be validated [74].
CONCLUSIONS
The environmental effect of aluminium depends on the form in which it occurs
in natural waters. The direct measurement of specific forms in real samples is very
difficult. Thus a number of procedures have been developed to distinguish between
broad groups of aluminium species. A proposed procedures usually is based on
measuring Qperationally defined aluminium fractions, which are not alwayscoinci-
dent, and makes a direct comparison between the published results very difficult.
Several authors of the papers concerning alulIlinium speciation tried to obtain the
results for as many as possible aluminium fractions. However, in a many of cases the
complete knowledge of the distribution of Al is not needed. There seems to be a
general agreement that the most reactive and toxic aluminium forms are A1
3
+,
AIOH
2
+, AI(OH)! and Al in very labile complexes (mainly inorganic). These species
are included in the inorganic monomeric fraction determined spectrophotometrically
with a short reaction time. They are also measured in exchangeable inorganic AI'
group. Therefore, for the evaluation of the chemical behaviour of aluminium in
natural aquatic systelTIS, colloidal Al must be given a consideration because it can
represent an essential fraction of this metal in freshwater [16].
Aluminium speciation
Acknowledgement
This work has been partially supported by the Tubitak-Doprog (Turkey) research grant.
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Received May 1998
AcceptedJuly 1998