Analytica Chimica Acta 431 (2001) 209218

Use of microwave single extractions for metal fractionation in

sewage sludge samples
B. Prez Cid, A. Fernndez Albors, E. Fernndez Gmez, E. Falqu Lpez
Depto. Qumica Analtica y Alimentaria, Facultad de Ciencias de Ourense, Universidad de Vigo, As Lagoas s/n, 32004 Ourense, Spain
Received 4 July 2000; received in revised form 26 September 2000; accepted 22 November 2000

Abstract
In the present study the original Tessier sequential extraction method has been applied for metal fractionation in sewage
sludge samples collected from an urban wastewater treatment plant and from one domestic olive oil factory. The results
obtained by this conventional method were compared with those estimated from direct microwave single extractions, in
order to reduce the conventional treatment time and simplify the experimental task. Microwave extraction conditions (heating
time and power) were specifically optimised for Cu, Cr, Ni, Pb and Zn with the aim of obtaining similar results to that of
the original Tessier method. Extractable metal contents obtained by both compared methodologies were measured by flame
atomic absorption spectrometry (FAAS). In the three first fractions of the Tessier method, the analytical results were similar
to those obtained from microwave single extractions for most of the elements in the two samples studied. In contrast, the
fourth fraction could not be directly extracted using the microwave procedure and must be leached from the solid residue of
the reducible fraction, using a two-step procedure. The overall extraction efficiency obtained by both single and sequential
microwave extractions were similar for all metals (recoveries between 93.9 and 102.3%), except for Cu in the two samples
studied and for Cr in the olive oil sludge (OOS) (recoveries <32%). The precision of the proposed microwave single extraction
method was <8.5% for all metals in the two samples. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Microwave single extraction; Sequential extraction; Heavy metals; Sewage sludge; Flame atomic absorption spectrometry

1. Introduction application is limited by the level of several conta-

The increasing amount of sewage sludge from
wastewater treatment plants constitutes a serious
problem of pollution when they are discharged on the
environment. The recycling of these wastes for agri-
cultural use is a useful alternative to incineration since
they can act as a source of nutrients for crops due to
their high organic matter content [1]. However, this
Corresponding author. Tel: +349-88-387081;
fax: +349-88-387001.
E-mail address: efalque@uvigo.es (E. Falque Lopez).
minants, such as toxic heavy metals, which may enter
into the human food chain through the consumption
of cultivated plants or contaminated waters, causing
risks for human health.
Total metal determination in sludge supplies valu-
able information about the overall pollution levels,
but is insufficient to estimate their biological effects,
which depend on the chemical species of the metals in
the sludge. An experimental approach frequently em-
ployed to study the mobility, transport and bioavail-
ability of metals in different types of environmental
samples (soils, sediments, sludges, etc.), is the use of

0003-2670/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 0 ) 0 1 3 3 5 - 0
210 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218
multi-step sequential extraction methods [2]. One of
the most widely applied is that proposed by Tessier
et al. [3] or modifications of this [4,5], where the met-
als are distributed among the following fractions: ex-
changeable, carbonates-bound, FeMn oxides-bound,
organic matter-bound and residual. The more mobilis-
able metals correspond to the two first fractions, which
can be released simply by increasing the ionic strength
and by slight pH changes.
The fractionation methods provide relevant infor-
mation about the possible metal content that could
be released on the environment. However, generally,
they do have some disadvantages [6,7] such as limited
reagent selectivity, re-adsorption among phases dur-
ing the extraction and intensive experimental labour
due to the slow and tedious extraction steps. Accord-
ing to Tack et al. [8], the fractions of the Tessier
method could be estimated from single extractions
employing reagents and operating conditions similar
to these of the different Tessier steps, but using a
separate sub-sample for each reagent. In this case, the
experimental task is considerably simplified, since
all fractions are simultaneously extracted and the
results are obtained faster. However, a larger sam-
ple is needed, which does not suppose an additional
problem in the study of environmental samples.
In our previous work [9], the Tessier and BCR se-
quential extraction methods were estimated from sin-
gle extractions and satisfactory results were attempted
from the simplified approach. However, in our opin-
ion, the single extraction procedure could be improved
by using microwave irradiation, recently applied for
acceleration of different chemical processes [10,11],
including multi-step sequential extraction methods
[1216]. So, this energy could be introduced to replace
the magnetic shaking and conventional heating in the
single step extractions, in order to shorten the treat-
ment time. Therefore, the main objective of this work
was to compare, in sewage sludge samples, the results
obtained using the conventional Tessier method with
that attempted from microwave single extractions cor-
responding to each individual fraction. The samples
studied were an urban sewage sludge (USS) and a
food-industrial sludge from a domestic olive oil pro-
cessing plant. Microwave operation parameters (heat-
ing time and power) were optimised for Cu, Cr, Ni, Pb
and Zn in each single extraction stage and in each case
the most favourable conditions were selected for them
all. Flame atomic absorption spectrometry (FAAS)
was used for the measurement of metals in the extracts.
2. Experimental
2.1. Instrumentation
Metal determination in the extracts was carried
out by means of a double beam Perkin-Elmer atomic
absorption spectrometer model 2380. Hollow cathode
lamps were used as radiation sources. The reso-
nance lines employed were 324.8, 357.9, 230, 217
and 213.9 nm for Cu, Cr, Ni, Pb and Zn, respec-
tively. Lamp intensity and bandpass width were used
according to the manufacturers recommendations.
Air/acetylene flow rate was 11/1 l min1 for all the
elements, except for Cr, where a more reducing flame
was required (11/2 l min1 ). A domestic Nevir cutter
was used for a fast reduction of sample particle size.
A domestic microwave oven (Moulinex, 900 W) was
used as a microwave radiation source. A centrifuge
(Kubota 5100) was used for a complete separation of
the extracts. A Crison 2000 pH meter was used for
pH adjustments in the extracts.
2.2. Reagents
The extractant solutions (listed in the protocol of
the Tessier method [3]) were prepared from analy-
tical grade reagents (Merck). Stock metal solutions
(1000 g ml1 ) for atomic absorption spectrometry
were obtained by dissolving the pure metal (in the
case of Cu and Zn) or the appropriate salts (in the case
of Pb, Ni and Cr) and making up to a corresponding
volume with ultra-pure water. Standard calibration
solutions were made daily, by appropriate dilution
of the stock solutions. The hydroxylammonium chlo-
ride was prepared prior to use. Dilute nitric acid and
ammonia solutions were used for pH adjustments.
2.3. Sample collection and pre-treatment
The USS sample was collected in polyethylene con-
tainers from an urban wastewater treatment plant next
to the town of Ourense (Spain). The olive oil sludge
(OOS) was collected, in a similar way, from an olive
oil factory located in the province of Jan (Spain). The
 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218 211

Table 1
Operational conditions required in the sequential Tessier method and in the microwave single extractions
Stage Fraction Reagent Shaking time
and temperature
Sequential Tessier method
1 Exchangeable 8 ml MgCl2 1 mol l1 (pH 7) 1 h at 25 C
2 Carbonate-bound 8 ml NaOAc 1 mol l1 (pH 5) 5 h at 25 C
3 FeMn oxides-bound (or reducible) 20 ml NH2 OHHCl 0.04 mol l1 in 25% (w/v) HOAc 6 h at 96 C
4 Organic matter-bound (or oxidizable) 3 ml HNO3 0.02 mol l1
5 ml H2 O2 30% (w/v) 2 h at 85 C
3 ml H2 O2 30% (w/v) 3 h at 85 C
5 ml NH4 OAc 3.2 mol l1 30 min at 25 C
5 Residual HNO3 /HCl/HF 26 min
Microwave single extractions
1 Exchangeable 8 ml MgCl2 1 mol l1 (pH 7) 80 s at 75 W
2 Carbonate-bounda 8 ml NaOAc 1 mol l1 (pH 5) 40 s at 170 W
3 FeMn oxides-bound (or reducible)a 20 ml NH2 OHHCl 0.04 mol l1 in 25% (w/v) HOAc 80 s at 170 W
4 Organic matter-bound (or oxidizable)b 3 ml HNO3 0.02 mol l1
5 ml H2 O2 30% (w/v)
3 ml H2 O2 30% (w/v) 15 s at 75 W
5 ml NH4 OAc 3.2 mol l1 10 s at 75 W
5 Residual HNO3 /HCl/HF 26 min
a These fractions were obtained by subtracting the metal content extracted in two consecutive microwave single fractions.
b This fraction was extracted from the solid residue of the microwave single reducible fraction.

samples were dried at 110 C in a heater to constant
weight. After this, they were ground using a Nevir
cutter, equipped with metallic blades, as it was proved
in a previous study [9] that this process does not in-
crease the extractable metal content in the sample. The
samples were then sieved, using a nylon fibre sieve,
and the sludge with particle size <70 m was sepa-
rated, homogenised, and stored in polyethylene bottles
at room temperature in a desiccator.
2.4. Sequential extraction scheme
The Tessier sequential extraction method was ap-
plied, in triplicate, to 2 g of pre-treated sludge samples
(<70 m). The reagents and operating conditions are
listed in Table 1. The extraction was carried out in
50 ml of polyethylene tubes also used for centrifuga-
tion to minimise the possible loss of sample in the
centrifuge-washing steps. After each extraction step
the supernatant was separated from the solid phase
by centrifugation at 2500 rpm for 5 min. It was then
decanted into polyethylene vessels and stored at 4 C
before analysis. The remaining residue was washed
with 10 ml of ultra-pure water, shaking for 15 min,
and the washings were discarded after centrifugation.
2.5. Microwave single extractions
Single extractions have been carried out employ-
ing a separate sub-sample (2 g) for each individual
step (Table 1). Each sub-sample was placed in 50 ml
polyethylene tubes and extraction was performed with
the suitable extractant under the microwave conditions
established in Table 1. Centrifugation and extracts
storage were performed similarly to the previous se-
quential extraction scheme, but the solid residue was
discharged.
Exchangeable metals were directly obtained since
they constitute the first fraction of the Tessier method.
Metals bound to the successive phases: carbonates
and FeMn oxides were evaluated by subtracting
the amount of leached metals in the exchangeable
and carbonate fractions (stages 1 and 2) from those
in carbonate and FeMn oxides (stages 2 and 3),
respectively.
Metals bound to organic matter and sulphides
cannot directly be leached from the corresponding
sub-sample due to the hydrogen peroxide boiling
under microwave action, so the fraction is alter-
natively extracted from the solid residue of stage
three.
212 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218

Percentages of metal recovery from each stage was
calculated as follows:
[MSE]
recovery (%) = 100
[CTM]
where [MSE] is the concentration determined by
microwave single extraction and [CTM] is that deter-
mined by the conventional Tessier method.
3. Results and discussion
3.1. Influence of microwave heating time
The effect of microwave heating time on metal
leached in the three first fractions was evaluated by
comparing the results obtained using the conventional
procedure with that of heating the extraction mixture
(reagent/sample) in the microwave oven for between
10 and 80 s, at 75 W. Prior to the heating step, the solid
sample and the extractant were homogenised using a
magnetic shaker for 5 s and the final solidliquid mix-
ture was immediately exposed to microwaves. In the
fourth fraction, the heating times ranged from 5 to 35 s
at 75 W, in order to avoid hydrogen peroxide boiling
over the vessel. The final treatment with NH4 OAc, in
this fraction, was fixed at 10 s since longer treatment
times caused excessive foaming of the extract.
The results of this study are shown in Fig. 1(A)(D).
It is important to emphasise that the influence of mi-
crowave parameters (heating time and power) was only
evaluated in the USS sample and the best microwave
extraction conditions thus, obtained were applied to all

Fig. 1. Influence of microwave heating time on the extraction efficiency: (A) first stage; (B) second stage; (C) third stage; (D) fourth stage.
 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218
the studied samples. Analytical methodology for de-
termination of extractable metals by FAAS in sewage
sludge samples is described in detail elsewhere [17].
As can be seen in Fig. 1, in the third and fourth frac-
tions all the elements studied appeared at a detectable
level when FAAS was used. In contrast, Cr and Pb
in the first fraction and Cr in the second fraction can-
not be quantified using this analytical methodology.
Ni and Pb were extracted, in all fractions, with simi-
lar results to the conventional Tessier method, except
for Pb in the third fraction, where only ca. 77% of the
metal content corresponding to this fraction was re-
leased. The percentage recovery achieved for these el-
ements (with the exception of Pb in the third fraction)
was close to 100% in all cases, using microwave heat-
ing times of >20 s in the first and third fractions, be-
tween 40 and 70 s in the second fraction and using only
15 s in the fourth fraction. In the last fraction, the ex-
traction efficiency of these elements was considerably
increased when the heating time was prolonged. How-
ever, in the three first fractions the extraction efficiency
was little changed when the heating time was varied.
Zn was also extracted according to the conventional
procedure in the first and fourth fractions (Fig. 1(A)
and (D)), using heating times between (5080) and
15 s, respectively. In the second and third fractions
(Fig. 1(B) and (C)), a low extraction efficiency was
obtained for Zn using the proposed procedure. The
best percentage recovery achieved was ca. 56 and 77%
in the second and third fractions, respectively. In both
cases, the recovery for this element was scarcely in-
creased when the heating time was prolonged.
In the case of Cu, the extraction efficiency of the
proposed procedure was, in most fractions, consi-
derably lower than to that obtained using the con-
ventional method. It was true in the first, second
and fourth fractions, where the percentage recoveries
were <50% in both cases. In the second fraction,
even a negative recovery value was obtained because
the extraction efficiency achieved using the proposed
procedure was inferior to that obtained in the ex-
changeable fraction. Moreover, in this same fraction,
when the microwave heating time was prolonged, the
recovery of this element was considerably reduced.
In the third fraction, either Cu and Cr were strongly
leached reaching abnormally elevated recovery per-
centages, which partially declined when the treatment
time was extended. This reduction was not signifi-
213
cant for Cu, but in the case of Cr it was. Therefore,
the percentage of recovery for the last element was
reduced to 94.9%, using a heating time of 80 s. A
reduction on the extraction efficiency was also ob-
served for Cr in the fourth fraction. The elevated
extraction efficiency found for Cu could be attributed
to the microwave heating, which will improve the Cu
extraction, leaching one part of metal corresponding
to the next fraction. Moreover, the particular decrease
affecting Cu and Cr microwave extraction, in the pre-
viously indicated fractions, could be explained by a
re-adsorption process, which was enhanced when the
microwave treatment was increased. This same effect
was also found in other studies [13,15,16], where mi-
crowave heating replaced the conventional treatment
in the sequential Tessier method.
It is possible to conclude, therefore, that by using
direct microwave extraction at 75 W for 80 s on the
first and third fractions, for 40 s for the second fraction
and for only 15 s for the fourth fraction, quantitative
recoveries can be obtained. These recoveries are for
Cr, Ni, Pb and Zn in the fourth fraction, for Cr and
Ni in the third fraction, for Ni and Pb in the second
fraction and for Ni and Zn in the first fraction. The
extraction efficiency was too low for Zn in the second
fraction, for Pb and Zn in the third fraction and for
Cu in all fractions, except the third, where Cu was
excessively leached. The anomalous results obtained
for Cu were also observed, for the same element, in
a previous work [16] where the Tessier method was
accelerated with microwave energy in each one of the
sequential steps. In this case, the authors also found
that Cu was poorly leached in the first, second and
fourth fractions and strongly leached in the third, when
microwave energy was employed.
3.2. Influence of microwave power
The influence of microwave power was evaluated
with the object of improving the extraction efficiency
of the accelerated procedure in those cases where this
is required, but using the most favourable microwave
heating times for each element and fraction. The
power values considered were 75, 122 and 170 W and
the extraction process was similar to that mentioned
above. Power values higher than 170 W were not used,
in order to avoid possible losses of sample caused by
the splashing of boiling solution over the vessel.
214 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218

Fig. 2. Influence of microwave power on the extraction efficiency: (A) first stage; (B) second stage; (C) third stage; (D) fourth stage.

The results of this study are shown in Fig. 2(A)(D).
As can be seen in these graphs, the variation of power
from 75 to 170 W did not provide quantitative recov-
eries for Cu in any fractions studied. Surprisingly, in
the three first fractions, the amount of metal leached
was considerably reduced when the extraction power
was increased (Fig. 2(A)(C)). This behaviour was
only advantageous in the third fraction, where this
element was excessively released and in which a
greater reduction of the extraction efficiency will be
needed. In the fourth fraction (Fig. 2(D)), the per-
centage recovery for Cu was scarcely changed when
the microwave power was varied.
In contrast, this study could be considered as ap-
proved for Zn in the second fraction and for Pb
and Zn in the third fraction. In both cases, the ex-
traction efficiency of these elements was consider-
ably enhanced as the microwave power increased
from 75 to 170 W. Thus, working at 170 W, quan-
titative recoveries were achieved for all of them
(Fig. 2(B) and (C)). For the rest of the cases, the
extraction efficiency was slightly modified when the
microwave power was varied within the considered
interval.
Finally, the best microwave operating conditions for
the extraction of all the elements studied, in the first
and third fractions, were achieved by heating for 80 s
at 75 and 170 W, respectively. The second and fourth
fractions must be extracted using a microwave irradia-
tion time of only 40 and 15 s and a microwave power of
 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218
170 and 75 W, respectively. These selected microwave
extraction conditions are listed in Table 1.
3.3. Comparison between analytical results obtained
by the conventional Tessier method and those
estimated from direct microwave single extractions
The conventional Tessier method and the mi-
crowave single extractions proposed in this work were
applied for metal partitioning in USS and in a domestic
OOS. The extraction was carried out in triplicate and
the analytical results obtained for Cu, Cr, Ni, Pb and
Zn are summarised in Table 2. In addition, the total
extractable metal content (sum of the four extractable
fractions) obtained by the conventional Tessier method
and microwave single extractions are shown in
Table 3.
As can be observed in Table 2, in the three first
fractions of the Tessier method, the results attempted
from microwave single extractions for Ni, Pb, Cr and
Zn were in good agreement with those obtained using
the sequential procedure for the two samples stud-
ied. The recoveries achieved varied between 90.6 and
104.2%. Cu presents a different behaviour in the two
samples studied. In the USS, and according to the
previous optimisation, it was poorly extracted in the
two first fractions and excessively leached in the third
fraction, when the proposed procedure was employed.
In contrast, in the OOS it was extracted according to
the conventional method in the three fractions (recov-
eries between 95.7 and 102.4%). In general, in the
two samples the microwave extraction was similar
for all metals, except for Cu, where different results
were displayed when the proposed microwave proce-
dure was employed. This could be attributed to the
different matrix composition of both samples.
As was explained previously, the fourth fraction
of the Tessier method should be released from the
remaining residue of the third fraction, even when
direct microwave extraction procedure is employed.
In this case, the recoveries achieved ranged from 96.8
to 107.5% for all metals, except for Cu in the two
samples studied (recoveries <23%) and for Cr in the
OOS, where it was not extracted when the microwave
procedure was used. Once more the Cr showed a
different behaviour in the two samples studied. This
could also be explained in a similar manner to Cu in
the three first fractions.
215
According to the above it can be concluded that
some significant differences were found in the metal
fractionation by the two extraction methods, and even
a different behaviour was found for some metals (Cu
and Cr) in the two samples studied. However, the over-
all metal extraction efficiencies are in good agreement
for most of the elements (Table 3). So, the total metal
leached using both methodologies was similar for Ni,
Pb and Zn in the two samples studied and also for Cr in
the USS (recoveries between 93.9 and 102.3%). This
means that for these elements, the environmental infor-
mation attempted from microwave single extractions
and the sequential method could be considered as sim-
ilar. In contrast, Cu and Cr in the OOS and Cu in the
USS were poorly leached using the proposed approach
(recoveries <32%).
The precision of the proposed microwave sin-
gle extraction method was evaluated in terms of
between-batch determinations (expressed as R.S.D.,
n = 3). The values obtained were always <8%
in the OOS and <8.5% in the USS, which means
that the method can be considered sufficiently
precise.
The total metal content in both sewage sludge sam-
ples (USS, OOS) was determined using a microwave
digestion procedure optimised and validated in a pre-
vious study [18]. The results obtained in USS were
442.74 4.35, 21.55 3.17, 37.32 2.64, 396.39
12.07 and 882.447.19 g g1 for Cu, Cr, Ni, Pb and
Zn, respectively. Analogously, the results obtained for
the same elements in OOS were 50.191.25, 59.04
3.45, 45.325.31, 23.101 and 70.101.27 g g1 .
In all cases, the results are expressed as mean values
(g g1 )S.D. of three separated determinations. Ac-
cording to this data it is possible to conclude that Cu,
Pb and Zn are the most abundant elements in the USS,
in contrast to the larger amounts of Cr and Ni that are
present in the OOS.
By taking into account the distribution of metals
within the Tessier extractable fractions (Table 2) and
the total metal content in the samples, it is possible
to predict a low mobility for Cu, Cr, Ni and Pb in the
two sludges studied. This is because these metals are
mainly associated with the residual and organic matter
fractions (between 74 and 100% of the total content).
In contrast, a higher bioavailability is expected for Zn,
which is mainly distributed among the non-residual
fractions (between 70 and 80% of the total content)
216 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218
 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218 217

Table 3
Total extractable metal contents obtained in USS and OOS samples using the conventional Tessier method and microwave single extractions
Element Total extractable metalsa (g g1 ) Recoveryb (%)

Conventional Tessier method Microwave single extractions

Urban sewage sludge (USS)

Cu 315.43 4.31 99.53 3.54 31.55
Cr 5.14 0.24 5.09 0.17 99.03
Ni 11.95 0.26 11.85 0.36 99.16
Pb 54.24 0.95 55.48 0.66 102.3
Zn 679.89 9.57 659.18 9.37 96.95
Olive oil sludge (OOS)
Cu 37.80 0.59 3.84 0.04 10.16
Cr 22.78 1.14 ndc
Ni 22.52 0.59 21.77 0.54 96.67
Pb 3.75 0.06 3.78 0.16 100.8
Zn 41.89 2.16 39.33 2.04 93.89
aSum of metals extracted in the four stages (expressed as g g1 ).
bRecovery is calculated as (MSE/CTM) 100, where MSE is the metal content extracted using microwave single extractions and
CTM is the metal content extracted by the conventional Tessier method.
c nd: not detected.

and specially associated with FeMn oxides (ca. 50%)
in the two samples.
4. Conclusions
Sequential extraction methods are usually employed
to evaluate the possible mobility and bioavailability
of toxic heavy metals present in environmental sam-
ples (sludges, sediments, soils, etc.). In general, they
are slow and tedious, little used for routine analysis,
because of their lengthy treatment times. In this way,
the microwave single extractions that are proposed in
this work could be considered as a useful alternative
to the conventional Tessier procedure in the study of
extractable metals from sewage sludge samples.
According to the reported results, the proposed
approach allows us to obtain similar results to the con-
ventional procedure, for most of the elements, but sub-
stantially reducing the operational time. In fact, in the
three first fractions, the shaking time has been reduced
from 1, 5 and 6 h to 80, 40 and 80 s of microwave
heating, respectively. An additional advantage of the
proposed procedure is that all fractions could be ex-
tracted simultaneously, and in this case the washing
steps after each sequential extraction stage are not
required, which also supposes a reduction of the final
treatment time. Similarly to the sequential method,
the fourth fraction must be leached from the solid
residue of the reducible fraction and, consequently, a
two-step procedure is required. In this case the con-
ventional treatment was reduced from 6 h to merely
15 s and it should be indicated that the tedious control
of temperature was also eliminated. Furthermore, the
final treatment with NH4 OAc for metal extraction of
the oxidised surface of the sludge, was also reduced
from 30 min to 10 s using the microwave procedure.
Despite some differences observed in the extraction
efficiency, the use of microwave single extractions
provides satisfactory results for Ni, Pb and Zn in
the two samples studied and also for Cr in the USS
sample. In contrast, Cu and Cr in the OOS and Cu in
the USS were not extracted as well when using the
proposed procedure. This means that the application
of microwave single extractions provides a promising
approach to obtaining rapid information about the
environmental impact of heavy metals.
Acknowledgements
The authors acknowledge the financial support
(Project 64102K007) of the University of Vigo
(Spain).
218 B. Perez Cid et al. / Analytica Chimica Acta 431 (2001) 209218
References
[1] S.R. Smith, Agricultural Recycling of Sewage Sludge and the
Environment, CAB International, Wallingford, 1996.
[2] A.M. Ure, C.M. Davidson, Chemical Speciation in the
Environment, Blackie, Glasgow, 1995.
[3] A. Tessier, P.G.C. Campbell, M. Bisson, Anal. Chem. 51
(1979) 844.
[4] G. Rauret, R. Rubio, J.F. Lpez Snchez, Int. J. Environ.
Anal. Chem. 36 (1989) 69.
[5] H.A. Elliot, B.A. Dempsey, P.S. Maille, J. Environ. Qual. 19
(1990) 330.
[6] J.R. Lead, J. Hamilton Taylor, W. Davison, Sci. Tot. Environ.
209 (1998) 193.
[7] J.L. Gmez-Ariza, I. Girldez, D. Snchez Rodas, E. Morales,
Anal. Chim. Acta 399 (1999) 295.
[8] F.M.G. Tack, H.A.H. Vossius, M.G. Verloo, Int. J. Environ.
Anal. Chem. 63 (1996) 61.
[9] A. Fernndez Albors, B. Prez Cid, E. Fernndez Gmez,
E. Falqu Lpez, Analyst 125 (2000) 1353.
[10] F.E. Smith, E.A. Arsenault, Talanta 43 (1996) 1207.
[11] Q. Jin, F. Liang, H. Zhang, L. Zhao, Y. Huan, D. Song,
Trends Anal. Chem. 18 (1999) 479.
[12] K.I. Mahan, T.A. Foderaro, T.L. Garza, R.M. Martnez, G.A.
Maroney, M.R. Trevisonno, E.M. Willging, Anal. Chem. 59
(1987) 938.
[13] M. Gulmini, G. Ostacoli, V. Zelano, A. Torazzo, Analyst 119
(1994) 2075.
[14] M. Ginepro, M. Gulmini, G. Ostacoli, V. Zelano, Int. J.
Environ. Anal. Chem. 63 (1996) 147.
[15] E. Campos, E. Barahona, M. Lachica, M.D. Mingorance,
Anal. Chim. Acta 369 (1998) 235.
[16] B. Prez Cid, I. Lavilla, C. Bendicho, Anal. Chim. Acta 378
(1999) 201.
[17] B. Prez Cid, I. Lavilla, C. Bendicho, Analyst 121 (1996)
1479.
[18] I. Lavilla, B. Prez Cid, C. Bendicho, Fresenius J. Anal.
Chem. 361 (1998) 164.