Talanta 80 (2009) 974979

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Talanta
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Determination of total arsenic and arsenic (III) in phosphate fertilizers and

phosphate rocks by HG-AAS after multivariate optimization based on
Box-Behnken design
Samuel M. Macedo a,b , Raildo M. de Jesus a,b,c , Karina S. Garcia d , Vanessa Hatje a,b ,
Antonio F. de S. Queiroz d , Sergio L.C. Ferreira a,b,
a
Instituto de Qumica, Universidade Federal da Bahia, CEP 40170-270, Salvador-BA, Brazil
b
Instituto Nacional de Cincia e Tecnologia, INCT, de Energia e Ambiente, Universidade Federal da Bahia, 40170-290 Salvador-BA, Brazil
c
Universidade Estadual de Santa Cruz, Departamento de Cincias Exatas e Tecnolgicas, CEP 45650-000, Ilhus-BA, Brazil
d
Universidade Federal da Bahia, Instituto de Geocincias, Ncleo de Estudos Ambientais, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In the present paper, a procedure for the determination of total arsenic and arsenic (III) in phosphate
Received 21 July 2009 fertilizers and phosphate rocks by slurry sampling (SS) with hydride generation atomic absorption
Received in revised form 19 August 2009 spectrometry (HG-AAS) is proposed. Arsenic (III) is determinated directly and total arsenic is deter-
Accepted 20 August 2009
minated after reduction reaction. The procedure was optimized for the ow rate of NaBH4 , NaBH4
Available online 28 August 2009
and hydrochloric acid concentrations using a full two-level factorial and also a Box-Behnken design.
Slurry preparation with hydrochloric acid in an ultrasonic bath allowed the determination of arsenic
Keywords:
(III) with limits of detection and quantication of 0.1 and 0.3 g L1 , respectively. The precision of
Multivariate optimization
Slurry sampling
results, expressed as relative standard deviation (RSD), was always lower than 3%. The accuracy of
Phosphate rocks this method was conrmed by analysis of certied sediment reference materials, while the procedure
Phosphate fertilizers also allows for calibration using aqueous external standards. This method (SS/HG-AAS) was used to
Arsenic determine total arsenic and arsenic (III) in two phosphate rock samples and two phosphate fertilizer
Hydride generation samples. In these samples, total arsenic concentrations varied from 5.2 to 20.0 mg kg1 , while As (III)
Atomic absorption spectrometry concentrations varied from 2.1 to 5.5 mg kg1 , in agreement with published values. All samples were also
analyzed using acid digestion/HG-AAS. Both, a paired t-test and a linear regression model demonstrated
no signicant difference (95% CL) between the results obtained using these two sample preparation
procedures.
2009 Elsevier B.V. All rights reserved.

1. Introduction and cadmium contamination of rainwater, groundwater, and soil

Arsenic is a highly toxic element, and arsenic exposure is
a serious concern worldwide. Several studies have shown that
the widespread use of phosphate rock in fertilizers is a signi-
cant source of arsenic contamination and exposure [1,2]. A study
of 196 fertilizer samples from 12 European countries concluded
that these fertilizers and the phosphate rock used to produce
them were signicant sources of arsenic, chromium, cadmium
and lead [3]. Chen et al. [4], evaluated arsenic and cadmium
exposure from the application of phosphate fertilizers to agricul-
tural soils, while another study demonstrated adverse impacts
from arsenic, antimony and lead in phosphorus-based fertiliz-
ers [5,6], and Mirlean and Roisenberg found signicant arsenic
Corresponding author at: Instituto de Qumica, Universidade Federal da Bahia,
CEP 40170-270, Salvador-BA, Brazil. Fax: +55 71 32355166.
E-mail addresses: slcf@ufba.br, sergio1057@hotmail.com (S.L.C. Ferreira).
in the area surrounding a phosphate fertilizer factory [7]. These
studies underscore the importance of measuring and controlling
arsenic inputs to soil from fertilizers prepared with phosphate
rocks.
The toxicity of arsenic compounds is highly dependent on their
speciation and valence state. Trivalent (As III) forms are more toxic
than pentavalent (As V) forms, while inorganic arsenic species tend
to be more toxic than organic forms [8,9]. Considering the high
prevalence of As in phosphate rocks and fertilizers, as well as the
role of chemical speciation in determining arsenic toxicity, opti-
mizing rapid, low-cost analytical procedures for determining the
concentration and speciation of arsenic in phosphate fertilizers and
rocks is of great importance. In this work, a rapid method for the
inorganic speciation of arsenic in phosphate fertilizers and phos-
phate rocks using slurry sampling is presented. Currently, several
analytical techniques exist for determining arsenic concentration
and speciation with adequate selectivity, accuracy, precision and
sensitivity. These techniques include hydride generation atomic

0039-9140/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2009.08.025
 S.M. Macedo et al. / Talanta 80 (2009) 974979 975

absorption spectrometry (HG-AAS) [1012], electrothermal atom- 2. Experimental

ization atomic absorption spectrometry (ET AAS) [13,14], hydride
generation atomic uorescence spectrometry (HG-AFS) [15,16],
and inductively coupled plasma mass spectrometry (ICP-MS)
[1719]. However, sample preparation and decomposition can
present signicant problems, particularly for solid sample matrices
[20]. This step is further complicated by the volatility of arsenic,
which requires that all acid digestion procedures be performed
in closed systems to reduce losses. Several efcient sample pre-
treatment methods already exist for the determination of arsenic,
including closed-vessel microwave-assisted digestion [21,22], in-
line digestion systems [23,24] and others. Currently, solid sampling
is the preferred technique for arsenic determination in solid matri-
ces, due to the complete elimination of the sample pre-treatment
step [25]. However, this technique requires specialized instru-
mentation that is not always available. Procedures involving this
technique have been proposed for the determination of arsenic in
barites [26] and sediments [27] employing electrothermal atomic
absorption spectrometry (ET AAS) as a detection technique. When
the required instrumentation for the above techniques is not avail-
able, slurry sampling [28,29] presents an excellent alternative,
eliminating the need of sample pre-treatment and reducing the
risk of analyte loss or contamination. Methods for As speciation
analysis using slurry sampling have been reported [30]. Consid-
ering the advantages of the slurry sampling technique, several
methods have been proposed for the determination of arsenic in
solid matrices. Table 1 shows some of these methods published
[3042].
In this paper it has been proposed a procedure for quantication
of total arsenic and arsenic (III) in phosphate fertilizers and phos-
phate rocks employing slurry sampling (SS) and hydride generation
atomic absorption spectrometry (HG-AAS). Arsenic (III) is deter-
minated directly and total arsenic is determinated after reduction
reaction.
2.1. Instrumentation
Arsenic concentrations were measured using a Varian model
SpectrAA 220 (Mulgrave, Victoria, Australia) ame atomic absorp-
tion spectrometer with an arsenic hollow cathode lamp. The
absorption wavelength was set at 193.7 nm, and measurements
were made using a lamp current of 10 mA and slit width of 0.5 nm.
A deuterium lamp was used for background correction. The ame
composition was acetylene (2.0 L min1 ) and air (13.5 L min1 ). An
Alitea C-6 XV peristaltic pump (Stockholm, Sweden) tted with
Tygon tubing was used to propel all solutions. High purity (99.99%)
argon was used as a purge gas, with a ow rate of 100 mL min1 .
For arsenic determinations, a quartz T-tube cell with a path-length
of 165 mm and a diameter of 12 mm was heated to approximately
900 C. Sample slurries were sonicated at room temperature using
a VWR model 75D ultrasonic bath.
2.2. Reagents
All reagents used were of analytical grade, and all solutions were
prepared using Milli-Q water (18.2 M cm1 ). A standard stock
solution of 1000 mg L1 As (III) was prepared by dissolving 0.1320 g
of As2 O3 in 25 mL of 1 mol L1 KOH solution. This solution was neu-
tralized with 2 mol L1 H2 SO4 and diluted to 100 mL with deionized
water. The stock solution was stored at 4 C. Working solutions of
arsenic (0.35.0 g L1 ) were prepared daily by diluting aliquots of
the stock solution with deionized water. A solution of hydrochlo-
ric acid (6 mol L1 ) was prepared from concentrated HCl (37%, v/v,
Merck). Aqueous solutions of 2% (w/v) sodium tetrahydroborate
were prepared freshly daily by dissolving solid NaBH4 in 0.5% (w/v)
NaOH before 0.45 m membrane ltration. Pre-reducing solutions
containing 10% (w/v) potassium iodide and 2.0% (w/v) ascorbic acid

Table 1
Methods proposed for the determination of arsenic using slurry sampling.

Sample Detection technique Calibration Slurry preparation Precision (%) Reference

Sediments HG-AAS DCAS Aqua regia + HF <13 31

CRM

Coal ET AAS <8.9 32

Environmental and biological ET AAS TSA HCl + ozone <7.8 33

CRM

Soil HG AFS DCAS HCl <4.5 34

CRM

Sediment ETV-ICP-MS SRM HNO3 + HF <8 35

Sediment and soil ET AAS DCAS <3.8 36

CRM

Soil HG-AAS TSA HCl <5 37

Fish ETV-ICP-MS DCAS <11 38

CRM

Sediment HG-AAS DCAS HNO3 + triton X-100 <8.5 39

CRM

Cigarette tobaccos HG-AAS DCAS HNO3 <7.6 40

CRM

Soil and sediment ET AAS TSA HF <5.5 41

DCAS
CRM

Soil and sediment ETVICP OES TSA <5.1 42

DCAS
CRM

TSA, technique of standard additions; DCAS, direct calibration against aqueous standards; CRM, certied reference materials.
976 S.M. Macedo et al. / Talanta 80 (2009) 974979
were prepared freshly daily in distilled water. A citric acid/sodium
citrate buffer (0.5/0.5 mol L1 , pH 7.1) was prepared freshly daily in
water. Two marine sediment reference materials for trace metals,
MESS-2 and MESS-3 (National Research Council of Canada, Ottawa,
Canada) were used for method calibration and validation.
2.3. Samples
Two commercial phosphate fertilizer samples (Superphosphate
Simple) and two phosphate rocks (from Algeria and Brazil) were
analyzed as described below.
2.4. Slurry preparation
Slurries were prepared by combining 0.1 g of dry, granular
sample material (particle size range: 20100 m) with 3.0 mL of
6.0 mol L1 hydrochloric acid in a 25 mL ask and immersing this
mixture in an ultrasonic bath for 30 min before diluting to 25 mL
with Milli-Q water. All reagent blanks were prepared in exactly
the same way as sample slurries. Aqueous standards were used to
generate standard calibration curves.
2.5. Sample preparation using a digester block
In order to evaluate the accuracy of the slurry sampling method,
triplicate samples were also prepared via temperature-controlled
acid digestion. Briey, 2 mL of concentrated nitric acid and 1 mL of
30% (v/v) hydrogen peroxide were sequentially added to 0.1 g of
each sample in a digester tube. Each tube was then tted with a
cold nger and heated at 100110 C for 4 h in a digester block
[43]. The resultant solution was diluted to 25 mL with Milli-Q
water.
2.6. Analytical procedure
2.6.1. Total arsenic
For determination of total arsenic, 3.33 mL of a 6 mol L1
hydrochloric acid solution, 1 mL of pre-reducing solution (KI
10% + ascorbic acid 2%) and aliquots of the sample slurries were
added to reaction asks. After 30 min, these resultant solutions
were diluted to 10 mL with Milli-Q water. Sodium tetrahydroborate
was introduced into the closed system at a rate of 2.70 mL min1
using a peristaltic pump, and the arsine vapor generated was trans-
ported to the AAS spectrometer using argon as carrier, with a ow
rate of 100 mL min1 . Calibration curves were generated by pro-
cessing aqueous As (III) standards (0.35.0 g L1 ) using the same
procedure.
For analysis of the digested samples aliquots of the sample solu-
tions were substituted by sample slurries.
Table 2
Full two-level factorial designoptimization of the procedure for HG.
Experiment [BH4 ] concentration % (w/v)
1 1.50 ()
2 2.50 (+)
3 1.50 ()
4 2.50 (+)
5 1.50 ()
6 2.50 (+)
7 1.50 ()
8 2.50 (+)
9 2.00 (0)
10 2.00 (0)
11 2.00 (0)
Results found using 10 mL of a 3.0 g L1 of arsenic (III) solution; FRB = ow rate of NaBH4 .
2.6.2. Arsenic (III)
For the determination of arsenic (III), aliquots of the samples
slurries were transferred to reaction asks containing 2 mL of citric
acid/sodium citrate buffer solution and diluted to a nal volume
of 10 mL with Milli-Q water. Sodium tetrahydroborate was intro-
duced into the closed system at a rate of 2.70 mL min1 using a
peristaltic pump, and the arsine vapor generated was transported
to the AAS spectrometer using argon as carrier, with a ow rate of
100 mL min1 .
For analysis of the digested samples aliquots of the sample solu-
tions were substituted by sample slurries.
3. Results and discussion
3.1. Optimization of the procedure for hydride generation
Optimization was conducted using 10.0 mL of 3.0 g L1 As (III)
solution and experiments were carried out in random order. Vari-
ables involved in the hydride generation step, including ow rate
of NaBH4 (FRB), NaBH4 concentration [BH4 ] and hydrochloric acid
concentration [HCl], were optimized using a two-level factorial
multivariate design. Experimental domains for each factor were
dened based upon literature data. Coded and real values, as well
as analytical signals (integrated absorbance), are shown in Table 2.
The concentrations of sodium hydroxide (0.5% w/v), pre-reducing
solution (potassium iodide and ascorbic acid) and the ow rate of
argon (100 mL min1 ) were selected based on literature values.
Effect coefcients calculated for each factor [44] were:
(+0.1109 0.0237), (+0.0672 0.0237) and (+0.0016 0.0237) for
[BH4], FRB and [HCl], respectively. The evaluation of these data
demonstrated that [BH4] and FRB were signicant factors, while
[HCl] was not. The positive sign of the signicant coefcients
indicated that integrated absorbance increased with increasing
borohydride concentration and ow rate as experimental domains
established for each factor. However, an Analysis of Variance
(ANOVA) indicated a poor t of these data to a linear model
(p = 0.086). A curvature test [45] was also applied, in which the
curvature was calculated using the equation: curvature = c, where
RFD is the average of the responses obtained from experiments
specied by the factorial design, and RCP is the average of the
responses obtained for the central point. An analysis of the results,
RFD = (0.1812) and RCP = (0.2392), suggests negative curvature, and
thus a maximum analytical signal in the region of the central point.
On the basis of these results, a Box-Behnken design [46,47] was
performed in order to t a quadratic model to the data and identify
the optimal conditions for the SS/HG-AAS procedure (Table 3).
This approach yielded the quadratic model:
R = 0.2390 + 0.0469[BH4 ] 0.0571[BH4 ]2 + 0.0632FRB
0.0413 FRB2 0.0301[HCl], which resulted in an improved t
(p = 0.1346). This model obtained has its maximum response
for the following experimental conditions: ([BH4 ] = 0.3178 and
FRB (mL min1 ) [HCl] concentration (mol L1 ) Integrated absorbance
1.00 () 1.00 () 0.0683
1.00 () 1.00 () 0.1679
3.00 (+) 1.00 () 0.2032
3.00 (+) 1.00 () 0.2016
1.00 () 3.00 (+) 0.0142
1.00 () 3.00 (+) 0.1655
3.00 (+) 3.00 (+) 0.2177
3.00 (+) 3.00 (+) 0.2371
2.00 (0) 2.00 (0) 0.2462
2.00 (0) 2.00 (0) 0.2308
2.00 (0) 2.00 (0) 0.2407
 S.M. Macedo et al. / Talanta 80 (2009) 974979 977

Table 3
Box-Behnken designoptimization of the procedure for HG.

Experiment [BH4 ] concentration % (w/v) FRB (mL min1 ) HCl concentration (mol L1 ) Absorbance

1 1.50 () 1.00 () 2.00 (0) 0.0164

2 2.50 (+) 1.00 () 2.00 (0) 0.1265
3 1.50 () 3.00 (+) 2.00 (0) 0.1854
4 2.50 (+) 3.00 (+) 2.00 (0) 0.2340
5 1.50 () 2.00 (0) 1.00 () 0.0822
6 2.50 (+) 2.00 (0) 1.00 () 0.2085
7 1.50 () 2.00 (0) 3.00 (+) 0.1130
8 2.50 (+) 2.00 (0) 3.00 (+) 0.2032
9 2.00 (0) 1.00 () 1.00 () 0.1256
10 2.00 (0) 3.00 (+) 1.00 () 0.2303
11 2.00 (0) 1.00 () 3.00 (+) 0.0949
12 2.00 (0) 3.00 (+) 3.00 (+) 0.2192
13 2.00 (0) 2.00 (0) 2.00 (0) 0.2392
14 2.00 (0) 2.00 (0) 2.00 (0) 0.2309
15 2.00 (0) 2.00 (0) 2.00 (0) 0.2469

Results found using 10 mL of a 3.0 g L1 of arsenic (III) solution.

2.15%), (FRB = 0.7040 and 2.70 mL min1 ) and ([HCl] = 0.0241 and
1.97 mol L1 ) (coded and real values, respectively). Critical points
were calculated as described previously [48]. The optimal delay
time for analytical measurements was found to be 15 s.
3.2. Optimization of the procedure for speciation of arsenic
from 2 mL of buffer masked the As (V) signal and hindered hydride
formation.
Optimal [HCl] for arsenic extraction was found to be 6 mol L1
for the extraction procedure described above, as illustrated by a
plot of absorbance vs. [HCl] (Fig. 2). At this concentration, recovery
was between 100 and 108%.

Effect of the addition of citric acid/sodium citrate buffer 3.3. Method validation
(0.5/0.5 mol L1 ) to standard solutions of As (III) and As (V) were
studied with concentrations on the order of g L1 . In the absence The SS/HG-AAS method described above was validated
of buffer, As (V) signal was observed (Fig. 1A), while the addition of according to IUPAC protocols [49]. HG-AAS signal was found

Fig. 1. Measure of the absorbance of  As (V) and As (III) in function of the time of analysis. 1A without addition of buffer in the solution of As (V). 1B, 1C and 1D with
addition of 1, 2 and 3 mL of the buffer, respectively.
978 S.M. Macedo et al. / Talanta 80 (2009) 974979

Table 4
Results of the determination of total arsenic after acid digestion and of total arsenic and As (III) in Marine Sediment Certicated Reference Material after slurry
sampling and acid digestion (n = 3).

CRM Certied values As total Acid digestion As total Slurry sampling As total Slurry sampling As (III)

(mg kg1 ) (mg kg1 ) RSD% (mg kg1 ) RSD% (mg kg1 ) RSD%

MESS-2 20.7 0.8 20.9 0.9 1.7 20.5 1.2 2.4 5.4 0.4 3.0
MESS-3 21.2 1.1 21.6 0.9 0.1 20.2 0.6 1.0 8.7 0.1 0.3

Fig. 2. Measure of the absorbance in function of the concentration of HCl. Fig. 3. Measure of analytical signal of As (III) and  As (V) in function of the time
after taken to a bath of ultrasound for 30 min.

to vary with arsenic concentration according to the equa-
tion: Abs = (0.0812 0.0024)CAs(mL g1 ) + (0.0193 0.0042),
r2 = 0.9993 within the linear range of 0.35.0 g L1 . The limits
of detection (3b/S) and quantication (10b/S) were calculated
as recommended by IUPAC [50], and were found to be 0.1 and
0.3 g L1 , respectively. These data are in good agreement with
the literature values [37,31,51,52].
Standards of As (III) and As (V) were taken to a bath of ultasound
for 30 min under the same conditions of samples. There was no
signicant change in the oxidation state of species after addition of
2 mL buffer (Fig. 3).
The precision (expressed as relative standard deviation) was
evaluated during analysis of the four samples, and was found to
be less than 8% in each case (Table 4).
The slope of the standard curve for arsenic concentration
was found to be (0.0816 0.0029) CAs and is quite comparable
with the slope obtained by the external calibration technique,
(0.0812 0.0024) CAs . These results demonstrate that the quanti-
cation of arsenic in phosphate matrices by slurry sampling can be
performed using the external calibration technique with aqueous
standard solutions.
The accuracy of the method was evaluated by analyzing marine
sediment reference materials: MESS-2 and MESS-3. The certied
total arsenic concentrations and the results obtained for As by
SS/HG-AAS are presented in Table 4. Measured total arsenic con-
centrations were in good agreement with certied values.
3.4. Applications
The SS/HG-AAS method was applied for the determination of
total arsenic and As (III) in two phosphate fertilizers and two
phosphate rock samples. In these samples, total arsenic concen-
trations varied from 5.2 to 20.0 mg kg1 and As (III) concentrations
varied from 2.1 to 5.5 mg kg1 . Measured total arsenic concentra-
tions were in good agreement with the literature values [53,54].
These results, expressed as 95% condence intervals, are presented
in Table 5. As a comparison to the SS-HG/AAS method, tripli-
cate samples were digested with hydrochloric acid and hydrogen
peroxide in a closed system prior to total arsenic determina-
tion by HG-AAS (Table 5). A statistical comparison using a paired
t-test [55] (95% condence level) showed no signicant differ-
ence between the results obtained by both methods. A linear
regression of the results obtained with the two methods fol-
lowed the equation [slurry sampling] = 0.959 0.046 [digestion
method] + 0.259 0.727, r = 0.9982.
These results demonstrate that the calculated slope and inter-
cept do not differ signicantly from the ideal values of 1 and 0,
respectively, and that there is no evidence for a systematic differ-
ence between the results obtained employing either procedure for
the determination of arsenic in the samples under study.

Table 5
Results of the determination of total arsenic and As (III) in phosphate fertilizers and phosphate rocks samples (n = 3).

Sample Acid digestion As total Slurry sampling As total Slurry sampling As (III)

(mg kg1 ) RSD% (mg kg1 ) RSD% (mg kg1 ) RSD%

SSP1 20.4 1.3 1.2 19.5 0.6 2.6 5.5 0.5 1.0
SSP2 13.0 2.9 8.0 12.6 2.5 9.0 7.5 1.0 5.2
PR1 5.1 0.2 1.8 5.2 0.2 1.8 3.9 0.2 2.5
PR2 20.2 1.5 1.3 20.0 0.6 3.0 2.1 0.2 4.6

SSP = phosphate fertilizer (superphosphate simple) and PR = phosphate rocks.

 S.M. Macedo et al. / Talanta 80 (2009) 974979
4. Conclusions
The SS/HG-AAS method demonstrated appropriate precision,
accuracy, and detection limits for the determination of arsenic
in phosphate rocks and phosphate fertilizer. In this work, slurry
sampling was found to be a useful extraction technique, particu-
larly given the volatility of arsenic species and the low solubility
of phosphate matrices in acid media. Arsenic concentrations
found in the four samples analyzed agreed with the literature
values for phosphate rocks and commercial phosphate fertiliz-
ers.
Acknowledgements
The authors would like to acknowledge the support of Fundaco
de Amparo a Pesquisa do Estado da Bahia (FAPESB), Conselho
Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq) and
Coordenaco de Aperfeicoamento de Pessoal de Nvel Superior
(CAPES).
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