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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+ +-+ AIOH2+~A12(OH)~+ ~ AI3(OH)~+ ~ AI8(OH)~O AI1304(OH)~t ~
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 A13+, AIOH2+ 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 A13+. Since
fluoride concentration in natural waters is generally lower than that of aluminium,
mainly Alp2+ and AIF2+ 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.
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 temperatur~.[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 were.used~Under 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 ratherthan,ad~orption1:>Y the container,material.
" On,e of the most controversial proble,~sconnected with aluminiumspeeiation
an~lysis 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-
niurn adsorbed onto~uspendeds,olids (clays, or colloidal particles of humic and fulvic
substC;lnces) is relatively labile 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 suspen~ed soilscont~nt and small filter pore size used.
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
b~cause 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.
Aluminium speciation 5
Analytical speciation
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 fra~tionationis shown in Figure 1. After
addition ofhydroxylamin~ and 1,IO-phenantroline for decreasing F~(III)interferen
ces, a~uminium species react within 2.3 s ~ith 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 complex~s.. The
complexes with citrate, humic or fulvic acids and Alp2+ are not included' in~this
"quickly reacting" aluminium fraction. '
Sample
iD.jecti~n
Pump
Separator
Buffer
Oxine ----+o-L-:=:-..........- - - . , . . . , . .
Water
---+-"---"-+0--...... Extraction
coil (3m)
mllmin
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
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 Amax 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 subtracting total 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 conditione~,witha 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 a:lsob~en .applied in aluminium speciation schemes to distinguish be-
tween resin exchangeabl~ (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 Ca2+, Mg2+~nd ". H,+with th~,col1centratipns 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 betwee~ sample and resin [61,62] . However, .in the ba~ch ,
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 sch~me for determining .the speciation ~f 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.
aeid digestion
FiltratioD
~G
Acid-extractable
particulate Al
1 !
® Chelex
Totalfilterable
Al
Nonexchangeable
filterable Al
~
®
Nonexchangeable
filterable Al
Figure 2. Fractionation scheme for speciation of aluminiuln (based on the procedure from [62])
" .v
,--. ,_.
. tI
Repeat...
Blank elution
peaks I------------~
-O.2+------+----__- ..........---......jI--....----I
o 5 10 15
Time, min
0.6
CD Non column-
o reactive AI
c: 0.4
as
.0
a-
o
U) 0.2
.0
<C.
o
Blank elution
..... O.2.....__p_e_a+~s ..... ......_ _. . . . . . j I _ _ _ -.....
o 2 4 6 8 10
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
Els~vier Science - NL)
10 K. Pyrzynska et aL
-=u
0
~
0.07
0.06
0.35
-=
.S
...
(I,)
Qj
0.05
0.30 "!-l
~
U
Qj
~
"'t:S
en
~ en
0,04 0.20
<
~ 0.03 0.15 ~
2- ~
(I,)
c.J
0.02 0.10 Qj
=
Cd
"Q 0,01 0.05
u
I::
t't:I
I-i ..0
0 J-c
en 0.00 0.00 0
..c V.1
< -0,01 -0.05
,.Q
<
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]
CONCLUSIONS
Acknowledgement
This work has been partially supported by the Tubitak-Doprog (Turkey) research grant.
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