Food Chemistry 149 (2014) 203207

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

A new method for preconcentration and determination of mercury in

sh, shellsh and saliva by cold vapour atomic absorption spectrometry
Valfredo Azevedo Lemos , Liz Oliveira dos Santos
Universidade Estadual do Sudoeste da Bahia, Laboratrio de Qumica Analtica (LQA), Campus de Jequi, Jequi, BA 45206-510, Brazil

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

Article history: The development of a method using solid phase extraction for preconcentration and determination of
Received 6 July 2013 mercury by cold vapour atomic absorption spectrometry is described. Hg (II) ions are sorbed on a mini-
Received in revised form 18 October 2013 column packed with Amberlite XAD-4 sorbent functionalised with 2-(20 -benzothiazolylazo)-p-cresol
Accepted 24 October 2013
(BTAC). Then, a reducing solution was used for desorption and the transport of the analyte for subsequent
Available online 1 November 2013
detection. The assay presented a limit of detection of 0.011 lg L1 (0.011 lg g1, for solid samples), a
limit of quantication of 0.038 lg L1 (0.038 lg g1, for solid samples), a precision of 0.50% (1.000 lg L1
Keywords:
Hg solution) and an enrichment factor of 46. The proposed method was applied to the determination of
Mercury
Cold vapour
mercury in human saliva (0.0550.200 lg L1). The following seafood collected in Todos os Santos Bay,
Preconcentration Brazil was also analysed: bass (0.1690.195 lg g1), mullet (0.0430.361 lg g1), shrimp
Functionalised resin (0.0750.374 lg g1) and mussel (0.2060.397 lg g1).
Seafood 2013 Elsevier Ltd. All rights reserved.
Saliva

1. Introduction man health. Most of this contamination comes from industrial

Mercury and its various chemical forms are known as species.
The most important species of mercury are elemental mercury
(Hg0), inorganic (Hg+ and Hg2+) and organic mercury (methylmer-
cury and ethylmercury). Mercury is most often present in the inor-
ganic form Hg2+ throughout the Earths crust. Dental amalgam is
one of the most commonly used restorative materials for posterior
teeth in dentistry. Despite widespread use, this amalgam contains
mercury, the use of which has undergone some restrictions due to
the toxic effects of this element (Rupp & Paffenba, 1971). Some
researchers have reported an increase in mercury release from
dental amalgams after dental restoration (Vimy, Takahashi, &
Lorscheider, 1990). Human saliva is one of the most important u-
ids used as a biomarker of exposure to chemical pollutants (Wang,
Du, & Zheng, 2008). Due to their toxicity and bioaccumulation,
quantication of mercury levels in several matrices including hu-
man saliva is extremely important (Shao et al., 2013; Wang et al.,
2008).
Fish and shellsh are often exposed to toxic substances such as
mercury because the aquatic environment is highly susceptible to
contamination by industrial discharge. In many regions, the sea-
food is the main source of income of the population (da Silva
et al., 2008). However, contamination of some aquatic environ-
ments hinders the availability of marine species, thus affecting hu-
Corresponding author. Tel./fax: +55 73 35289630.
E-mail address: vlemos@uesb.edu.br (V.A. Lemos).
activities that rely on chemicals toxic to health, including mercury.
Thus, biomonitoring of toxic elements such as mercury in matrices
such as marine foods, natural waters and sediments is crucial.
Chronic exposure to mercury causes toxic effects even at trace
concentrations because it can cause irreversible neurological dam-
age. Due to these health risks, there is great interest in the devel-
opment of sensitive and reliable analytical techniques to
determine mercury content. Various detection techniques are cur-
rently available, such as cold vapour atomic absorption spectrom-
etry (CV AAS), inductively coupled plasma optical emission
spectrometry (ICP-OES) and electrothermal atomic absorption
spectrometry (ET AAS) (Leopold, Foulkes, & Worsfold, 2010; Tuzen,
Karaman, Citak, & Soylak, 2009). Despite instrumental advances,
some techniques do not have adequate sensitivity and selectivity
for the determination of this element in a large number of matri-
ces. Thus, separation and enrichment of the analyte are usually re-
quired prior to analysis. Different materials and analytical
strategies have been developed for this purpose (da Silva, Portugal,
Serra, Ferreira, & Cerda, 2013; Leopold et al., 2010; Tuzen, Uluozlu,
Karaman, & Soylak, 2009).
Solid phase extraction has been widely used in the separation
and preconcentration of various species. There are many advanta-
ges to this technique, such as simplicity, reliability, reduction in
analysis time, reduction or elimination of the use of organic sol-
vents and a high potential for automation (Behbahani et al.,
2013; Teixeira, Costa, Assis, Ferreira, & Korn, 2001). Some reagents
may be associated with supports for solid phase extraction by two

0308-8146/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.10.109
204 V.A. Lemos, L.O. dos Santos / Food Chemistry 149 (2014) 203207
different methods: (1) by formation of a chemical bond between
the reagent and the polymeric matrix (functionalised sorbents)
(Lemos, Santos, & Nunes, 2005), and (2) by impregnation of the
binder matrix, employing a solution containing the reagent (loaded
sorbents) (Amorim & Bezerra, 2007; Soylak, Elci, Narin, & Dogan,
2001). The second method is simpler in practise. However, this
functionalisation enables a long lifetime for the solid phase be-
cause of covalent bonds between the ligand and the support be-
cause the leaching of the ligand molecule associated with the
solid support is sharply reduced (Camel, 2003).
Polyurethane foam (Abdel-Azeem, Bader, Kuss, & El-Shahat,
2013; Cassella et al., 1999), silica gel (Rudner, Pavon, Rojas, & de
Torres, 1998), alumina (Ahmed, 2008) and polystyrene divinylben-
zene (Amorim & Bezerra, 2007) are widely used as supports for the
immobilisation of ligands. Chelating reagents are usually anchored
to supports through AN@NA, ACH2A, and AN@CA linkages
(Persaud & Cantwell, 1992; Saxena, Singh, & Sambi, 1994). The an-
chored ligand can increase the sorption capacity of these materials,
which favours the extraction of metal ions in solution and may also
acquire specicity for a metal ion, reducing the time for sorption
equilibrium (Camel, 2003).
This work aims to develop a sensitive, rapid and economical
method for the determination of mercury in various matrices using
detection by CV AAS and preconcentration employing Amberlite
XAD-4 (polystyrenedivinylbenzene) resin functionalised with
BTAC as a sorbent.
2. Experimental
2.1. Instrumentation
The absorbance measurements were performed using an atomic
absorption spectrometer (Perkin Elmer model AA400, USA)
equipped with hydride generator system. An electrodeless dis-
charge lamp (EDL) was used as radiation source of Hg
(253.65 nm). Electrothermal atomic absorption spectrometry was
carried out using a HGA 900 (Perkin Elmer) model graphite fur-
nace, coupled to spectrometer. The equipment was operated under
the following temperature conditions: drying I: 100 C (ramp
5 C s1, hold 25 s); drying II: 140 C (ramp 15 C s1, hold 15 s);
pyrolysis: 250 C (ramp 10 C s1, hold 20 s); atomizing: 1100 C
(ramp 0 C s1, hold 5 s); cleaning: 2600 C (ramp 1 C s1, hold
5 s). Measurements of cold vapour atomic absorption spectrometry
were carried out under the following conditions: slit 0.7 nm; argon
ow rate 70 mL min1; carrier solution 3.0% (v/v) HCl; read time
20 s; peak height signal mode.
The pH of the solutions was monitored using a pH metre model
Q400AS (Quimis, Brazil). The digestion of solid samples was per-
formed using acid digestion bombs and microwave digestion
bombs models 4749 and 4781 (Parr, USA), respectively. A peristal-
tic pump model 204 (Milan, Brazil) and silicone and PTFE tubes
were also used in the preconcentration procedure.
2.2. Reagents
Ultrapure water obtained from a water purication system
(Elga Purelab Classic model, Bucks, UK) was used to prepare all
solutions. Working solutions of mercury (lg L1) were prepared
by diluting a 1000 lg mL1 solution of the element (Merck, Ger-
many) with ultrapure water. Amberlite XAD-4 (SigmaAldrich,
Brazil) was used to prepare the functionalized sorbent
(XAD-BTAC). The reagent BTAC. (Lemos & Ferreira, 2001) and the
sorbent XAD-BTAC (Lemos et al., 2005) were prepared in the labo-
ratory according to procedures described previously. A 2.0% (w/v)
sodium borohydride (SigmaAldrich) in 0.2 mol L1 NaOH solution
was used in the hydride generator system. The pH of Hg solutions
was adjusted with the aid of acetic acid/sodium acetate
(pH 4.04.7), phosphate (pH 6.0), boric acid/sodium hydroxide
(pH 7.58.5) and ammonium (pH 9.010.0) buffer solutions (Per-
rin, 1974). The certied reference materials BCR 482 Lichen, BCR
414 Plankton and ERM-CE278 Mussel tissue (Institute for Refer-
ence Materials and Measurements, Belgium) were used to study
the accuracy of the method.
2.3. Sample preparation
2.3.1. Human saliva and certied reference material
Saliva samples (approximately 6.0 mL) were collected from
healthy volunteers aged between 20 and 25 years. These samples
were stored under refrigeration and immediately transported to
the laboratory. An aliquot of 2.0 mL (or 0.100 g of certied refer-
ence material) sample was transferred to a Teon cup of acid
digestion bomb. Nitric acid (65% w/v, 4.0 mL) and hydrogen perox-
ide (30% v/v, 1.0 mL) were added. The digestion bomb ask was
closed and placed in an oven at 75 C for 6 h. After cooling to room
temperature, the pH was adjusted with NaOH solution. The digest
was transferred to a 100.0 mL volumetric ask containing 20.00 mL
of the buffer solution, and then, the ask was lled to the mark
with ultrapure water.
2.3.2. Seafood
The samples were collected in the municipality of So Francisco
do Conde (specically, the village of Muribeca). Muribeca is located
in Todos os Santos Bay, Bahia, Brazil. The seafood used was: bass
(Centropomus undecimalis), mullet (Mugil brasiliensis), shrimp
(Penaeus brasiliensis) and mussel (Mytella guyanensis). Samples
(0.1 g) were weighed and transferred to Teon cups in order to
microwave the acid digestion bombs. Next, 2.0 mL of 65% (w/v) ni-
tric acid and 1.0 mL of ultrapure water were added. The acid diges-
tion bomb was closed, and the system subjected to microwave
radiation for 60 s at a power of 100 W. After cooling and adjusting
the pH with an NaOH solution, the digest was transferred to a
100.0-mL ask containing 20.00 mL of buffer solution, Finally, the
ask was lled to volume with ultrapure water.
2.4. General procedure for preconcentration
Solutions (100.00 mL) containing Hg (II) at pH 8.0 were passed
through a minicolumn (0.30 cm internal diameter  8.0 cm length)
containing 0.20 g of XAD-BTAC at a ow rate of 5.50 mL min1.
After passing the whole solution containing Hg (II) through the col-
umn, a 1.75 mol L1 hydrochloric acid solution was used to desorb
the metal from the minicolumn. The eluate (2.50 mL) was collected
in a microtube, and the mercury content in the enriched phase was
measured by CV AAS.
3. Results and discussion
3.1. Optimization of conditions for the preconcentration
A 1.0 lg L1 Hg (II) solution was used in the optimization of
variables. The extraction of the element by XAD-BTAC was calcu-
lated using the following equation: E = (CV/CoVo)  100, where C
is the concentration of mercury in the eluate, V is the volume of
the eluent, Co is the initial concentration of mercury in the solution
passed through the minicolumn, and Vo is the volume of the mer-
cury solution that was passed through the minicolumn.
 V.A. Lemos, L.O. dos Santos / Food Chemistry 149 (2014) 203207 205

3.1.1. pH 100
pH plays an important role in the ligandmetal interaction, and
therefore, the inuence of pH on the preconcentration of Hg (II) 80
with XAD-BTAC was studied. The pH of the Hg (II) solutions was

Extraction (%)
varied in the range of 4.010.5. The maximum sorption of Hg (II) 60
occurred at pH 8.0, as illustrated in Fig. 1. In an acidic environment
the formation of the complex is not observed, possibly due to com- 40
petition with H3O+ in active sites of the sorbent. At pH values above
9.0 the signal decreases due to hydroxide formation, thereby
20
decreasing the formation of the mercury complex. Therefore, for
further experiments, a pH 8.0 was selected, using the borate buffer.
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
3.1.2. Sample ow rate Concentration of eluent (mol L-1)
Although high ow rates are required to achieve high enrich-
ment factors, the kinetics of the chelate complex-metal limit the Fig. 2. Inuence of concentration of eluent in preconcentration of mercury using
maximum ow rate. The sorption of Hg (II) on functionalized resin XAD-BTAC.
was studied at ow rates varying from 1.0 to 10.1 mL min1. The
best results were obtained when the ow rates were from 1.0 to
the mass of the sorbent was not sufcient to complex all the metal
6.6 mL min1. At ow values greater than 6.6 mL min1, the con-
present in the volume of sample that was passed through the mini-
tact time between the phases was insufcient, which did not allow
column. Consequently, the contact time of the solution with the so-
complete sorption. Thus, a ow of 5.5 mL min1 was established to
lid phase was not sufcient for a complete sorption. The use of a
provide a high sampling rate without compromising retention of
sorbent mass greater than 0.300 g resulted in an increase in pres-
Hg (II).
sure that was caused by excess in the solid phase, decreasing the
ow rate of the solution containing the sorbed species in the
3.1.3. Desorption studies
minicolumn.
To check the concentration of the eluent which allows total
The lifetime of the sorbent is an important factor in preconcen-
desorption of the metal from sorbent material the concentration
tration procedures using solid-phase extraction. Long-lifetime sor-
of HCl was varied between 0.00 and 2.50 mol L1. As can be seen
bents that maintain their performance over many cycles are
in Fig. 2, it was not possible to completely desorb the Hg (II) ions
desirable in solid phase extraction. This parameter was investi-
from the minicolumn when acid concentrations lower than
gated by monitoring the analytical response corresponding to a
1.75 mol L1 are used. At concentrations above 1.75 mol L1, there
minicolumn at the end of a working day and then counting the
is not signicant variation in the analytical signals. Thus,
number of preconcentration cycles. No signicant change was ob-
1.75 mol L1 hydrochloric acid solutions were used in subsequent
served in the extraction of Hg (II) for at least 400 cycles using the
experiments.
minicolumn packed with the sorbent XAD-BTAC.
The effect of the ow of eluent was examined in the range from
1.0 to 8.1 mL min1. The results shown that at ow rates below
5.5 mL min1, the eluent were transported by minicolumn so
3.2. Selectivity studies
slowly that the total desorption of the metal was not feasible.
Employing ow values between 5.5 and 8.1 mL min1, no signi-
To evaluate the selectivity of the procedure, the inuence of
cant variation on response was observed. Based on the results of
several ions on the preconcentration and determination of mercury
this study, the value of 6.6 mL min1 for the ow of the eluent
using the sorbent XAD-BTAC was studied. Solutions containing Hg
was used in all subsequent experiments.
(II) at 1.0 lg L1 and other species at various concentrations were
used in this study. The effect of a species was considered signi-
3.1.4. Amount and lifetime of sorbent
cant when their presence caused a variation greater than 5% in
The inuence of the amount of functionalized resin used in the
the value of the analytical response. According to the results shown
extraction of mercury was studied. The best results were obtained
in Table 1, the species Cd (II), Co (II), Mn (II), Ni (II) and Pb (II) inter-
when a mass of 0.200 g was used. Extraction was incomplete if
fere with the extraction of lower concentrations of Hg (II). It was
quantities of less than 0.200 g sorbent were used. In this case,
reported that these species form stable chelates with the reagent
BTAC (Lemos & Ferreira, 2001). Then, the cations most likely
100

Table 1
80 Effect of other ions on the determination of mercury using the proposed procedure.

Ion Amount (ng/mL) Extraction (%)

Extraction (%)

60 Mg2+ 50000 88
Fe2+ 50000 90
K+ 1000 99
40 Zn2+ 1000 99
Al3+ 1000 95
Cl 1000 106
20 Cd2+ 500 110
Pb2+ 500 92
Na+ 500 96
0
Ni2+ 500 90
3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0
Co2+ 500 103
pH Mn2+ 500 91
NO3 500 92
Fig. 1. Inuence of pH in preconcentration of mercury using XAD-BTAC.
206 V.A. Lemos, L.O. dos Santos / Food Chemistry 149 (2014) 203207

Table 2 occupy the active sites of the adsorbent, reducing the absorption of
Results for determination of mercury in certied reference material and saliva mercury. The other species tested did not interfere at any signi-
samples.
cant quantities.
Material Content of mercury found (lg g1) Error (%)
Certied Proposed method 3.2. Analytical features
Lichen BCR 482 0.48 0.02 0.478 0.012 0.4
Mussel tissue ERM-CE278 0.196 0.009 0.197 0.010 0.5 The analytical parameters that describe the developed method
Plankton BCR 414 0.276 0.018 0.279 0.014 1.1
were calculated under optimum conditions. The calibration graph
ETAAS Proposed method
Saliva 001a 0.110 0.020b 0.105 0.001b 4.8 obtained through a linear regression analysis is A = 0.1909C +
Saliva 002a 0.149 0.010b 0.145 0.002b 2.8 0.0107, where A is the absorbance and C is the concentration of
Saliva 003a 0.198 0.009b 0.200 0.001b 1.0 Hg (II) in lg L1. The equation corresponding to the analytical
Saliva 004a 0.143 0.001b 0.140 0.007b 2.1
curve for the direct measurement of mercury by CV AAS is
Saliva 005 <LQ <LQ
Saliva 006 <LQ <LQ
A = 0.0042C + 0.0217. The method is linear in the range of 0.038 a
Saliva 007 <LQ <LQ 1.000 lg L1.
Saliva 008 0.050 0.002b 0.055 0.003b 9.1 The limit of detection (LOD) of the method was calculated using
ETAAS: electrothermal atomic absorption spectrometry.
the equation LOD = 3Sb/b, where Sb is the standard deviation of the
a
Individuals using dental amalgam. background of the analytical signal obtained from 10 measure-
b
Results in lg L1. ments, and b is the slope of the corresponding analytical curve.
Similarly, the limit of quantication (LOQ) was calculated using
the expression LOQ = 10Sb/b. The limit of detection and limit of
quantication were 0.011 and 0.038 lg L1, respectively. The
Table 3 enrichment factor (EF) indicates the increase in the analytical sig-
Results for determination of mercury in seafood samples using the proposed
procedure.
nal provided by a preconcentration method. This parameter was
calculated by dividing the values of the slopes from analytical
Sample Content of mercury (lg g1) Recovery (%) curves obtained by the preconcentration procedure and direct
Added Found measurement, respectively (Fang, Dong, & Xu, 1992). The con-
Bass 1 0.0 0.195 0.02 sumptive index (CI), which denes the utilisation efciency of
0.5 0.670 0.06 95 the sample was calculated using the expression V = CI/EF, where
1.0 1.201 0.17 101 V is the volume of the solution of Hg (II) (Fang et al., 1992). The
Mullet 1 0.0 0.361 0.03
enrichment factor and consumptive index were 46 and 2.17 mL,
0.5 0.900 0.02 108
1.0 1.400 0.04 104 respectively. The precision of the method was expressed as the rel-
Shrimp 1 0.0 0.374 0.05 ative standard deviation, which is calculated by dividing the stan-
0.5 0.880 0.01 101 dard deviation of multiple measurements (S) and the mean of
1.0 1.380 0.07 101 measurements (x): RSD(%) = (S/x)  100. The precision obtained
Mussel 1 0.0 0.397 0.03
0.5 0.900 0.07 101
(n = 14) for a 1.000 lg L1 Hg solution was 0.50%.
1.0 1.380 0.09 98 In this work, the accuracy was evaluated by analysis of certied
Bass 2 0.0 0.169 0.02 reference material. The results are shown in Table 2. The t-test
0.5 0.669 0.02 100 showed that the results obtained with the proposed methodology
1.0 1.170 0.03 100
were not signicantly different at the 95% condence level.
Mullet 2 0.0 0.043 0.01
0.5 0.543 0.01 100
1.0 1.010 0.01 97 3.3. Application to real samples
Shrimp 2 0.0 0.075 0.01
0.5 0.580 0.02 101
1.0 1.107 0.02 103 Saliva samples were analysed using the proposed procedure.
Mussel 2 0.0 0.206 0.03 The content of Hg (II) in the samples was also quantied by ETAAS.
0.5 0.770 0.01 113 The results are shown in Table 2. Samples 14 are derived from
1.0 1.290 0 03 108
individuals who have mercury amalgam dental llings. Individuals
corresponding to samples 58 do not have this type of dental

Table 4
Characteristics of methods using solid phase extraction for preconcentration of mercury. LOD: limit of detection; EF: enrichment factor; PDCA: 2,6-pyridine dicarboxylic acid;
AATP: 2-aminoacetylthiophenol; 1,2-BAE: 1,2-bis(o-minophenylthio)ethane; PSDVB: polystyrenedivinylbenzene; ACPG: aminopropyl-controlled pore glass; PSTH: 1,5-bis
(2 pyridyl)-3-sulphophenyl methylene thiocarbonohydrazyde; DPTH: 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide; TS: methylthiosalicylate; BG: Brilliant Green; MB:
2-mercaptobenzimidazole; TC: thiosemicarbazide.

Ligand Support Detection technique LOD (lg/L1) EF Volume (mL) Sample Ref.
2,6-PDCA SiO2 ICP OES 0.09 175 350 Water Zhang et al. (2010)
AATP PSDVB ICP OES 0.23 300 3000 Water Guo et al. (2004)
1,2-BAE PSDVB CV AAS 0.09 259 Water Mondal and Das (2003)
PSTH ACPG CV AAS 0.01 28 14.4 Mussel Rudner et al. (1998)
CV ETAAS 0.006 42 14.4
TS Silica gel ICP OES 5.00 79 250 Water Hashemi-Moghaddam, Panahi, and Nezhati (2009)
BG PSDVB CV AAS 50 500 Water Sanz et al. (2004)
2-MB Agar CV AAS 0.02 250 Water and sh Pourreza and Ghanemi (2009)
TC Alumina CV AAS 10100 1000 Water Ahmed (2008)
BTAC PSDVB CV AAS 0.011 46 100 Saliva and seafood This work
 V.A. Lemos, L.O. dos Santos / Food Chemistry 149 (2014) 203207
restoration. The paired samples t-test was used to compare the
mean values obtained by ETAAS and the proposed method showed
no signicant difference at 95% level. The proposed procedure was
also applied to seafood samples. The mercury levels found in the
samples are presented in Table 3.
4. Conclusion
The proposed method for the determination of mercury proved
to be simple, efcient and easy to perform in the matrices ana-
lysed. The Amberlite XAD-4 functionalized with BTAC reagent,
which was efcient for the complexation of Hg (II) allowing extrac-
tion/preconcentration with a high enrichment factor. The proposed
procedure also presented analytical features (e.g., limit of detec-
tion, precision and accuracy) suitable for the determination of Hg
(II) in both saliva samples and in sh and shellsh. Table 4 shows
a comparison between the analytical characteristics of the pro-
posed method and some procedures described in the literature.
Acknowledgements
The authors acknowledge the nancial support of the Conselho
Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq) and
the Fundao de Amparo Pesquisa do Estado da Bahia (FAPESB).
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