Académique Documents
Professionnel Documents
Culture Documents
Analytical Letters
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lanl20
To cite this article: Li-Jiao Zhao , Ting Ren & Ru-Gang Zhong (2012): Determination of Lead in Human
Hair by High Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry with
Microwave Digestion and Solid Sampling, Analytical Letters, 45:16, 2467-2481
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.
Analytical Letters, 45: 24672481, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2012.689903
Atomic Spectroscopy
The content of lead in human hair was measured by high resolution continuum source graph-
ite furnace atomic absorption spectrometry (HR-CS GFAAS) combined with
microwave-assisted digestion (MAD) and direct solid sampling (DSS). Hair strands were
washed, dried, and then cut into three parts (root, middle portion, and tip). For
MAD-GFAAS assays, approximately 0.25 g of hair was completely digested using a mix-
ture of concentrated nitric acid and hydrogen peroxide in a closed system. In the
DSS-GFAAS assays, 0.10.2 mg of dried hair was directly introduced into a graphite fur-
nace using a solid autosampler. The temperature programs were optimized and the effects of
various added modiers were compared. The results indicated that NH4H2PO4 was the
optimal modier for analysis of Pb using GFAAS. Use of the optimal modier and tempera-
ture program gave similar limits of detection for MAD-GFAAS and DSS-GFAAS of
1.16 ng/g and 0.82 ng/g, respectively. Both methods also produced satisfactory recoveries
ranging from 98.69% to 103.14%. There was no signicant difference observed between
the Pb contents of hair strands determined by the MAD-GFAAS and DSS-GFAAS assays,
which both indicated that the Pb levels increased along the hair strands. Comparison of the
two methods revealed that DSS-GFAAS had several advantageous characteristics over
MAD-GFAAS, including the need for much less sample material and having a less
time-consuming procedure, lower sample blank absorbance, lower memory effect, and no
risk of environmental pollution by digesting chemicals. The direct solid sampling technique
can be employed as a good alternative to conventional wet digestion in AAS assays.
Keywords: Direct solid sampling; High resolution continuum source graphite furnace atomic absorption
spectrometry; Human hair; Lead; Microwave-assisted digestion
2467
2468 L.-J. ZHAO ET AL.
INTRODUCTION
The heavy metal lead has been reported to be highly toxic to animals and
humans, owing to their adverse effects on the hematopoietic, nervous, renal, and
skeletal systems (Verstraeten, Aimo, and Oteiza 2008; Kales, Christophi, and Saper
2007; Tokar, Diwan, and Waalkes 2010; Karimooy et al. 2010; Weaver et al. 2009;
Ronis et al. 2001). The central nervous system is one of the most important targets of
lead (Sidhu and Nehru 2004; Gu et al. 2009), and the neurotoxic effects of lead in
children have been shown to be higher than those in adults (Murata et al. 2009).
The human immune system can also be affected by lead exposure, which may lead
to some autoimmune diseases and alternation of the expression of CD4, CD8, and
CD16 (Mishra 2009).
Lead can accumulate in the human body via food and environmental exposure,
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
and the biological effects of lead depend on the level and duration of exposure
(Barrento et al. 2009; Hong et al. 2008; de Vries, Romkens, and Schutze 2007). A num-
ber of investigations have been conducted to investigate the Pb concentration in vari-
ous biological samples such as blood, tissue, serum, and urine as a means of evaluating
Pb exposure (R. S. Li et al. 2011; Yin et al. 2009; Xia et al. 2008). However, in most
cases, it is difcult to conduct direct measurements on blood or tissue samples from
humans. Human hair, which is more likely to be obtained than other human biological
materials, is considered to be a good material for investigation of the toxicity of heavy
metals from endogenous or exogenous sources (Grandjean 1984; Harikins and Susten
2003; Baysal and Akman 2010; Pozebon, Dressler, and Curtius 1999). Moreover,
because human hair has the capacity to store and to retain trace elements, hair samples
have been widely employed to investigate the toxicity of heavy metals over long periods
of time (Ni, Li, and Wang 2011; Shah, Kazi, Afridi, Kazi, et al. 2011; Li et al. 2011;
Shah, Kazi, Afridi, Khan, et al. 2011; Massadeh, El-Rjoob, and Smadi 2011; Olmedo
et al. 2010). Ni et al. (2011) measured the levels of seven metals (Mn, Cu, Zn, Pb, Cr,
Cd, and Se) in the scalp hair of residents who lived near Dexing Copper Mine, Jiangxi
Province, China. Shah, Kazi, Afridi, Kazi, et al. (2011) compared the levels of essential
and toxic elements in scalp hair, blood, and urine samples of anemic children, and
found that they had lower essential=toxic metal ratios than the control group. Y. H.
Li et al. (2011) assessed the trace element concentrations in the hair of 107 healthy
centenarians in China and found that their longevity was related with sufcient Zn
and Se concentrations, as well as low exposure to heavy metals pollution.
High resolution continuum source atomic absorption spectrometry (HR-CS-
AAS), which is a considerable innovation of traditional line source atomic absorp-
tion spectrometry (LS-AAS), achieves its high resolution by employing a double
monochromator with a prism for pre-dispersion and an echelle grating for highest
resolution (Welz et al. 2005; Welz et al. 2009). In recent years, HR-CS-AAS has been
frequently used in the determination of metal and nonmetal elements in biological
samples (El Deeb, Ma, and Gust 2012; de Campos et al. 2011; Quadros et al.
2011; Oliveira et al. 2010; Sardans, Montes, and Penuelas 2010). Previous investiga-
tions proved that HR-CS-AAS technique was adequate for the determination of lead
in biological samples because of its simplicity, high sensitivity, good accuracy, and
wide applicability (Borges et al. 2006). In this work, HR-CS-AAS was employed
for the determination of lead in human hair.
DETERMINATION OF LEAD IN HUMAN HAIR BY HR-CS GFAAS 2469
samples. Recently, DSS-GFAAS was employed in the analysis of trace metals in hair.
Borges et al. (2006) determined the concentration of lead in seven biological solid cer-
tied reference materials and demonstrated that the concentration of Pb in complex
matrices can be successfully assayed using direct solid sampling. Baysal and Akman
(2010) reported a rapid and practical solid sampling AAS method for determining the
ultra-trace lead concentration in very small amounts of hair. Using DSS-GFAAS,
Nomura and Oliverira (2010) obtained the longitudinal proles of Cd and Pb concen-
trations along a hair strand.
The goal of this study was to evaluate the method of DSS-GFAAS for deter-
mination of lead in hair by comparing its performance with that of conventional acid
digestion. This study is expected to provide an effective method for the trace analysis
of metal elements in biological samples.
EXPERIMENTAL
Apparatus
All measurements were conducted using a ContrAA 700 (Analytik Jena AG,
Jena, Germany) high resolution-continuum source atomic absorption spectrometer
(HR-CS AAS) equipped with a xenon short-arc lamp, a high-resolution double
echelle monochromator, and a CCD array detector. Transverse heating techniques
were used for the graphite furnace atomizer. An MPE-60 autosampler for liquid sam-
ples and an SSA600 autosampler for solid samples were installed for MAD-GFAAS
and DSS-GFAAS, respectively. High purity Ar (99.999%) was applied as the protec-
tive and purge gas at the ow rates listed in Table 1.
A BT-214D electronic balance (Sartorius, Germany) was used to weigh the
samples. In addition, an ETHOS A Microwave Digestion System (Milestone, Italy)
was used for digestion of the samples. The optimized graphite furnace parameters for
the determination of lead are given in Table 1.
Reagents
All reagents were of analytical grade (Sigma-Aldrich, USA), and all solutions
were prepared using deionized water produced by a PureLab Prime system (PALL,
USA). Certied reference materials (CRMs) of human hair (GBW 09101 and GBW
2470 L.-J. ZHAO ET AL.
Table 1. Optimized furnace heating programs for determination of Pb concentrations in human hair by
high resolution-continuum source GFAAS
Drying 90 3 20 90 3 20 1.2
Drying 110 5 10 110 5 10 1.2
Pyrolysis 800 300 30 650 300 40 1.2
Gas adaption 800 0 5 650 0 5 0
Atomization 1550 1550 4 2000 1500 5 0
Cleanout 2600 500 4 2600 500 4 1.2
20 mL of sample solution with 5 mL of 1% (w=v) NH4H2PO4 as a modier was used for optimization of
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
09101b) and 100 mg=L Pb stock solution were bought from the National Research
Center for Certied Reference Materials of China. All containers and glassware were
soaked in 5.0 mol=L HNO3 for at least 24 h and then rinsed three times with deio-
nized water prior to use. The working solutions were prepared daily from their stock
solutions using deionized water.
Procedure
MAD-GFAAS. Hair samples (length 30 cm) were collected from six female
donors aged 24 to 31. The fresh hair was cut from the scalp of the head. The hair sam-
ples were washed according to the procedure described by the International Atomic
Energy Agency (IAEA) (1978), which included once with acetone, thrice with deio-
nized water and once again with acetone, after which the samples were dried at
75 C. The hair strands were subsequently cut into three parts (the roots, the middle
portion and the tips) using a stainless steel scissor. Each part was about 10 cm long.
Next, approximately 0.25 g of dried hair sample was accurately weighed and added
into the polytetrauoroethylene (PTFE) digestion vessel together with 7 mL of con-
centrated HNO3 and 1 mL of H2O2. The samples were digested using a two-step tem-
perature program. In the rst step, the temperature was linearly increased to 190 C
over 10 min with the maximum power of the rotating magnetron at 1000 W. In the
second step, the temperature was kept at 190 C for 30 min. After digestion and cool-
ing, which took about 3 h, each solution was diluted to 50 mL with deionized water in
a volumetric ask, after which the analytes were determined by GFAAS. The results
were given as the average of three repetitive measurements, and all digestions were
conducted in triplicate.
The sample solutions obtained from MAD or the standard solutions made in
water containing 0.5% (v=v) HNO3 were injected into the graphite furnace atomic
absorption spectrometer together with the modiers. The temperature program is
shown in Table 1. The absorbance values at 283 nm were monitored to determine
the concentration of Pb. A 20 mL sample or standard solution accompanied by
5 mL of 1% (m=v) NH4H2PO4 as the modier was analyzed in each run.
DETERMINATION OF LEAD IN HUMAN HAIR BY HR-CS GFAAS 2471
DSS-GFAAS. The hair samples were cut into approximately 0.5 cm segments
that were appropriate to t into the cavity of the boat-type graphite platforms.
Approximately 0.10.2 mg of dried hair was loaded in the boat-type platform for
direct solid sampling. The SSA600 autosampler automatically weighs a sample using
an integrated microbalance with a precision of 1 mg, after which it is transported into
the graphite furnace. In this study, the solid autosampler was used not only for the
solid hair samples, but also for liquid standards to conduct calibrations. To maintain
the same working conditions for the hair samples and the standards, 20 mL of aqueous
standards and 5 mL of modiers were pipetted manually onto the same platform
to perform the calibration. The temperature program for the DSS-GFAAS is listed
in Table 1.
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
Figure 1. Pyrolysis and atomization curves for Pb in hair samples analyzed in the presence of various
amounts of NH4H2PO4 as modiers. (Figure available in color online.)
standards. Briey, a Pb stock solution (100 mg=L) was diluted to 100 mg=L as the
working solution. This working solution was then automatically diluted with 0.5%
(v=v) HNO3 solution to obtain a series of calibration working solutions with concen-
trations of 10.0, 20.0, 40.0, 60.0, and 80.0 mg=L. The linearity of the calibration curves
was evaluated based on the values of the correlation coefcients (R2). Two calibration
curves were automatically generated by the Aspect CS software (2008). One curve
is linear [Equation (1), R2 0.9997] and the other is nonlinear [equation (2),
R2 0.9999]. In this study, the concentration of Pb in the hair samples was deter-
mined using the nonlinear calibration equation.
y 0:004026x 0:026431 1
y 0:004655x 0:020991=0:001835x 1 2
40 mL) were added into the PTFE digestion vessels together with 7 mL of con-
centrated HNO3 and 1 mL of H2O2, after which they were digested using the same
temperature program that was used for the hair samples. Following digestion and
cooling, each sample was diluted to 50 mL with deionized water in a volumetric ask.
The concentrations of Pb in each sample were analyzed six times to determine the
precision and accuracy of the methods. The recovery was calculated as shown in
formula (3).
99.76% to 103.14% and the precision represented by the RSD ranged from 3.60%
to 7.20%. The recovery and precision indicate that the presented quantitation
method gives good reproducibility and the effect of the sample digestion procedure
on the measured Pb concentration is negligible.
The LOD was calculated from three times the standard deviation (SD) of the
reagent blank readings. The SD was obtained from 20 analyses of the reagent blank,
which only contained 0.5% (v=v) HNO3 and modiers, using the same temperature
program that was used for the samples. The limit of quantitation (LOQ) was based
on the same measurements used to determine the LOD, except using 10 times the SD
of the blank readings. The values of LOD and LOQ of the MAD-GFAAS method
were 1.16 ng=g and 3.87 ng=g, respectively. The LOD value obtained in this study by
using HR-CS-AAS was lower than that reported by Moreira, Borges, and ROliveira
(2005), who measured the Pb in lichens by line source ETAAS with an LOD of
5.4 ng=g using conventional heating block digestion and an LOD of 4.4 ng=g using
microwave oven digestion.
DSS-GFAAS
Selection of the matrix modifier. The temperature program was optimized
using various modiers. Based on the results of the modier addition during
MAD-GFAAS, 1% (m=v) NH4H2PO4 solution was used as a modier. Triton
X-100 was also added into the modier at a concentration of 0.05% (m=v), which
improved the interaction between hair segments and the NH4H2PO4 modier by
decreasing the surface tension of the solution (Nomura and Oliveira 2010). Moreover,
Figure 2. Pyrolysis and atomization curves for Pb in hair samples analyzed in the presence of various
chemical modiers as determined by DSS-GFAAS. (Figure available in color online.)
DETERMINATION OF LEAD IN HUMAN HAIR BY HR-CS GFAAS 2475
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
Figure 3. Comparison of the time-resolved absorbance spectra of Pb obtained using different modiers (a)
No modier; (b) 1% NH4H2PO4; (c) 0.5% Pd(NO3)2; (d) 1% NH4H2PO4 0.05% Triton X-100; (e) 1%
NH4H2PO4 0.5% Pd(NO3)2; (f) 1% NH4H2PO4 0.05% Triton X-100 0.5% Pd(NO3)2. (Figure
available in color online.)
y 0:000176x 0:015778 4
Figures of merit. The LOD and LOQ of the DSS-GFAAS assays were calcu-
lated according to the method proposed in previous studies (Baysal and Akman
2476 L.-J. ZHAO ET AL.
2010; Kurfurst 1998; Oleszczuk et al. 2007; Torok and Zemberyova 2010), which are
briey described as follows. The standard deviation (SD) was obtained from 20 read-
ings of the absorbance of a solid sampling platform containing only modiers. The
LOD was then calculated as the concentration corresponding to three times the SD.
The LOQ was obtained using the same method, but was calculated from ten times
the SD of the reagent blank measurements. The LOD and LOQ obtained using
various modiers are shown in Table 3. The values of the LOD ranged from 0.82
to 6.76 ng=g, and the values of the LOQ ranged from 2.74 to 22.54 ng=g. Owing to
the relatively high values of LOD and LOQ obtained in response to the addition
of Pd(NO3)2 and Triton X-100, the determination of Pb by DSS-GFAAS was also
conducted using only NH4H2PO4 as the modier. The sensitivity of the DSS-
GFAAS method using the optimal modier (NH4H2PO4) was higher than that of
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
the MAD-GFAAS method. The LOD obtained in this study (0.82 ng=g) was close
to that reported by Baysal and Akman (2010) (0.3 ng=g), while much lower than that
reported by Nomura and Oliveira (2010) (40 ng=g), who also determined the Pb con-
tent in human hair by DSS-GFAAS. Our results indicate that sufcient sensitivity
was achieved to satisfy the requirements for determination of Pb in biological
samples by using solid sampling together with HR-CS-AAS. The accuracy of the
method was investigated by determining the analytical recovery using certied refer-
ence materials (CRMs) of human hair, GBW 09101 and GBW 09101b. As shown in
Table 4, the recovery of the DSS-GFAAS method was 98.69102.64%, which indi-
cates that the determined concentrations were in good agreement with the certied
values.
Table 3. LOD and LOQ for DSS-GFAAS assay obtained using different chemicals as modiers (n 10)
Table 4. Contents of Pb in the certied human hair standards as determined by DSS-GFAAS (n 10)
Data were given as the average with 95% condence intervals.
The certicated samples (about 0.25 g) were digested and diluted to 50 mL, after which they were
subjected to GFAAS analyses via liquid sampling.
Second, DSS-GFAAS is much less time consuming because it requires no time for
digestion. Conversely, MAD includes pre-digestion, a temperature program in a
microwave oven and cooling, resulting in about 3 h being required to analyze one
batch of samples. Third, a lower sample blank absorbance was obtained when
DSS-GFAAS was conducted due to the great decrease of contamination as a result
of no digestion agents being needed. In the present study, the absorbance of sample
blanks in the DSS-GFAAS analysis was approximately 0.0050.008, while it was
0.0100.015 in the MAD-GFAAS analysis. Fourth, the memory effect of previous
samples could be avoided during DSS-GFAAS by cleaning the boat-type platform
between the assays of each sample. Finally, DSS-GFAAS does not cause environmen-
tal pollution, because no strong corrosive or toxic chemicals are used for digestion.
As mentioned in previous investigations (Baysal and Akman 2010; Nomura
and Oliveira 2010), the disadvantage of DSS-GFAAS was the relatively high
RSD, which may have been due to the loss of sample during transfer between the
balance and the furnace. In this study, this problem was effectively resolved and a
satisfactory RSD for DSS-GFAAS was obtained (0.74.0%) by keeping the sample
amount from exceeding half of the capacity of the boat-type platform and by repeat-
ing the analysis at least ve times for each run.
Pb content (mg=kg)
Hair Hair
strands No. segment MAD-GFAAS (n 3) DSS-GFAAS (n 5)
Data were given as the averages with 95% condence intervals.
(2010) found that the IAEA hair wash protocol (once with acetone, thrice with water
and once again with acetone) resulted in the determined contents of Pb increasing
along hair strands as determined in the present study; however, when the hair samples
were washed using the IAEA protocol combined with HCl, the Pb contents in the tips
were obviously decreased. Therefore, it can be assumed that the Pb content in hair
reected the level of both endogenic and exogenous Pb. Analysis of the hair strands
from the six donors revealed that the hair from donor No. 5 had the highest level of
Pb, which was likely a result of the donor dying her hair one month before the hair
samples were collected.
CONCLUSION
Determination of Pb content in human hair is an effective approach to reect
the levels of heavy metal exposure in vivo. In this study, GFAAS was employed to
measure the Pb contents in the root, middle and tip of human hair strands. Speci-
cally, GFAAS was conducted in conjunction with the microwave-assisted digestion
(MAD) and direct solid sampling (DSS) techniques. The results showed that there
was no signicant difference in the Pb contents determined by MAD-GFAAS and
DSS-GFAAS. Additionally, the two methods had similar sensitivity and accuracy.
However, DSS-GFASS required less time and sample amount than MAD-GFAAS.
Overall, the results presented here indicate that the DSS technique is a good alterna-
tive to conventional HNO3-H2O2 digestion for AAS analysis. Moreover, analysis of
human hair strands showed that the Pb content increased as the hair grew, which
might have been due to both biological and environmental factors. This study
DETERMINATION OF LEAD IN HUMAN HAIR BY HR-CS GFAAS 2479
provides effective methods for determining heavy metals in biological samples, and is
expected to shed light on the investigation of acute or chronic toxicity of heavy metals.
REFERENCES
Acar, O. 2005. Determination of lead, chromium, manganese and zinc in slurries of botanical
and biological samples by electrothermal atomic absorption spectrometry using tungsten-
containing chemical modiers. Microchim. Acta. 151: 5358.
Arslan, Z., and J. F. Tyson. 2007. Slurry sampling for determination of lead in marine
plankton by electrothermal atomic absorption spectrometry. Microchem. J. 86: 227234.
ASpect CS 1.5.3. 2008. Analytik Jena AG, Konrad Zuse Str. 1.
Barrento, S., A. Marques, B. Teixeira, M. L. Carvalho, P. Vaz-Pires, and M. L. Nunes. 2009.
Downloaded by [University of Chicago Library] at 02:34 19 June 2013
Accumulation of elements (S, As, Br, Sr, Cd, Hg, Pb) in two populations of Cancer pagurus:
Ecological implications to human consumption. Food Chem. Toxicol. 47: 150156.
Baysal, A., and S. Akman. 2010. Determination of lead in hair and its segmental analysis by
solid sampling electrothermal atomic absorption spectrometry. Spectrochim. Acta B 65:
340344.
Baysal, A., and S. Akman. 2011. A rapid solid sampling method for determination of nickel
and copper along human hair by ETAAS. Microchem. J. 98: 291296.
Biasino, J., J. R. Dominguez, and J. Alvarado. 2007. Hydrogen peroxide in basic media for
whole blood sample dissolution for determination of its lead content by electrothermal
atomization atomic absorption spectrometry. Talanta 73: 962964.
Borges, D. L. G., A. F. da Silva, B. Welz, A. J. Curtius, and U. Heitmann. 2006. Determi-
nation of lead in biological samples by high-resolution continuum source graphite furnace
atomic absorption spectrometry with direct solid sampling. J. Anal. Atom. Spectrom. 21:
763769.
De Campos, R. C., C. L. T. Correia, F. Vieira, T. D. Saint Pierre, A. C. Oliveira, and R.
Goncalves. 2011. Direct determination of P in biodiesel by high-resolution continuum
source graphite furnace atomic absorption spectrometry. Spectrochim. Acta B 66: 352355.
De Vries, W., P. Romkens, and G. Schutze. 2007. Critical soil concentrations of cadmium,
lead, and mercury in view of health effects on humans and animals. In Reviews of Environ-
mental Contamination and Toxicology, Vol. 191, ed. G. W. Ware. New York: Springer.
El Deeb, S., B. N. Ma, and R. Gust. 2012. Determination of Ni-II(3-OMe-salophene) in
MCF7 and HT29 cancer cell lines using HR-CS-AAS and in serum albumin using LC with
monolithic silica. Microchem. J. 101: 2429.
Grandjean, P. 1984. Lead poisoning: Hair analysis show the calendar of events. Hum. Exp.
Toxicol. 3: 223228.
Gu, C. W., S. J. Chen, X. J. Xu, L. K. Zheng, Y. Li, K. S. Wu, et al 2009. Lead and cadmium
synergistically enhance the expression of divalent metal transporter 1 protein in central
nervous system of developing rats. Neurochem. Res. 34: 11501156.
Gunduz, S., S. Akman, A. Baysal, and M. Kahraman. 2010. The use of silver nanoparticles as
an effective modier for the determination of arsenic and antimony by electrothermal
atomic absorption spectrometry. Spectrochim. Acta B 65: 297300.
Harikins, D. K., and A. S. Susten. 2003. Hair analysis: exploring the state of science. Environ.
Health Persp. 111: 576578.
Hong, C. L., Y. B. Jia, X. E. Yang, Z. L. He, and P. J. Stoffella. 2008. Assessing lead
thresholds for phytotoxicity and potential dietary toxicity in selected vegetable crops. Bull.
Environ. Contam. Tox. 80: 356361.
Agency, I. A. E. 1978. Activation analysis of hair as an indicator of contamination of man by
environmental trace element pollutants. Report IAEA=RL=50.
2480 L.-J. ZHAO ET AL.
Kurfurst, U. 1998. Solid sample analysis-direct and slurry sampling using GF AAS and
ETV-ICP. Berlin: Springer-Verlag.
Li, R. S., H. T. Yan, X. M. Yang, Z. X. Li, and Y. A. Guo. 2011. Simultaneous determination
of trace lead, tin and cadmium in biological samples by a chemical vapor generation-four-
channel atomic uorescence spectrometry dual gas-liquid separator system. J. Anal. Atom.
Spectrom. 26: 14881493.
Li, Y. H., L. S. Yang, W. Y. Wang, H. R. Li, J. M. Lv, X. Y. Zou. 2011. Trace element
concentrations in hair of healthy Chinese centenarians. Sci. Total. Environ. 409: 13851390.
Massadeh, A., A. W. El-Rjoob, and H. Smadi. 2011. Lead, cadmium, copper, zinc, iron, and
calcium in human hair as a function of gender, age, smoking, and hair dyeing. Toxicol.
Environ. Chem. 93: 494503.
Mishra, K. P. 2009. Lead exposure and its impact on immune system: A review. Toxicol. In
Vitro 23: 969972.
Moreira, F. R., R. M. Borges, and R. M. Oliveira. 2005. Comparison of two digestion
procedures for the determination of lead in lichens by electrothermal atomic absorption
spectrometry. Spectrochim. Acta B 60: 755758.
Murata, K., T. Iwata, M. Dakeishi, and K. Karita. 2009. Lead toxicity: does the critical level of
lead resulting in adverse effects differ between adults and children? J. Occup. Health 51: 112.
Ni, S. Q., R. P. Li, and A. J. Wang. 2011. Heavy metal content in scalp hair of the inhabitants
near Dexing Copper Mine, Jiangxi Province. China Sci. China Ser. D 54: 780788.
Nomura, C. S., and P. V. Oliveira. 2010. Method for cadmium and lead longitudinal proles
determination in hair by solid sampling graphite furnace atomic absorption spectrometry.
Anal. Methods 2: 4953.
Oleszczuk, N., J. T. Castro, M. M. da Silva, M. D. A. Korn, B. Welz, and M. G. R. Vale.
2007. Method development for the determination of manganese, cobalt and copper in green
coffee comparing direct solid sampling electrothermal atomic absorption spectrometry and
inductively coupled plasma optical emission spectrometry. Talanta 73: 862869.
Oliveira, S. R., J. A. G. Neto, J. A. Nobrega, and B. T. Jones. 2010. Determination of macro-
and micronutrients in plant leaves by high-resolution continuum source ame atomic
absorption spectrometry combining instrumental and sample preparation strategies. Spec-
trochim. Acta B 65: 316320.
Olmedo, P., A. Pla, A. F. Hernandez, O. Lopez-Guarnido, L. Rodrigo, and F. Gil. 2010.
Validation of a method to quantify chromium, cadmium, manganese, nickel and lead in
human whole blood, urine, saliva and hair samples by electrothermal atomic absorption
spectrometry. Anal. Chim. Acta. 659: 6067.
Pozebon, D., V. L. Dressler, and A. J. Curtius. 1999. Hair analysis: A review on the proce-
dures for the determination of trace elements and applications. Quim. Nova. 22: 838846.
DETERMINATION OF LEAD IN HUMAN HAIR BY HR-CS GFAAS 2481