ANALYTICAL

BIOCHEMISTRY
Analytical Biochemistry 339 (2005) 1–8
www.elsevier.com/locate/yabio

The improvement of sensitivity in lead and cadmium

determinations using flame atomic absorption spectrometry
Mehmet Yaman *

Department of Chemistry, Sciences and Arts Faculty, Firat University, 23119 Elazig, Turkey

Received 8 July 2004

Available online 1 February 2005

Abstract

Various designs of quartz tubes of the slotted tube atom trap were examined to improve the sensitivity of flame atomic absorp-
tion spectrophotometry. The studied designs include the diameter length and the length of the upper slot of quartz tubes. Tubes
having a diameter of 5 and 6 mm and an upper slot length of 2.3 cm produce the best sensitivity—as high as 6- and 10-fold enhance-
ment for lead (Pb) and cadmium (Cd), respectively. The limits of quantitation were found to be 35 and 4 ng ml
1 for Pb and Cd,
respectively, by the optimized method. The achieved technique was applied to determine the concentrations of Pb and Cd in can-
cerous (malign) and noncancerous (adenoma) human thyroid tissues.
Ó 2005 Elsevier Inc. All rights reserved.

Keywords: STAT; Sensitivity improvement; Flame atomic absorption spectrometry; Lead; Cadmium; Thyroid

It is well known that in either excess or deficiency, is known that the toxic and carcinogenic potentials of
certain trace metals in the living can lead to biological the metals depend largely on their solubilities and their
disorders. Lead (Pb)1 is known to be a toxic metal that displacements with the essential metals such as Zn,
accumulates in the human body throughout the lifetime. Mg, and Ca [3]. It was reported that Cd toxicity had
It was reported that Pb had not caused oxidative DNA been alleviated partially by high dietary concentrations
damage even in the presence of H2O2, but d-aminolevu- of Zn, Fe, and Ca [4]. The increased dietary concentra-
linic acid, which accumulates in Pb poisoning, had in- tions of Ca, P, Fe, Mg, Zn, and vitamin E also reduce
duced oxidative DNA damage and might participate the toxicity of Pb. The allowed concentrations of Cd
indirectly in Pb carcinogenesis [1]. Data related to the and Pb in biological samples are as low as the levels of
carcinogen effect of cadmium (Cd) are given in the liter- ng kg
1 or ng ml
1. The World Health Organization
ature in detail [2]. Occupational exposure to Cd is asso- (WHO) [5] established provisional tolerable weekly in-
ciated with lung cancer in humans. On the other hand, it takes (PTWIs) of Cd and Pb of 0.007 and 0.025 mg kg
1
body weight, respectively, for all human groups. There-
*
fore, analytical techniques with high sensitivity are re-
Fax: +90 424 233 0062.
E-mail address: myaman@firat.edu.tr.
quired for detection of these metals. These techniques
1
Abbreviations used: Pb, lead; Cd, cadmium; WHO, World Health include electrothermal atomic absorption spectrometry
Organization; PTWI, provisional tolerable weekly intake; ETAAS, (ETAAS), inductively coupled plasma–atomic emission
electrothermal atomic absorption spectrometry; ICP–AES, inductively spectrometry (ICP–AES), anodic stripping voltammetry
coupled plasma–atomic emission spectrometry; ASV, anodic stripping (ASV), differential pulse polarography (DPP), and induc-
voltammetry; DPP, differential pulse polarography; ICP–MS, induc-
tively coupled plasma–mass spectrometry; FAAS, flame atomic
tively coupled plasma–mass spectrometry (ICP–MS).
absorption spectrometry; STAT, slotted-tube atom trap; IARC, It is well known that flameless atomic absorption
International Agency for Research on Cancer. spectrometry is a more sensitive technique than flame

0003-2697/$ - see front matter Ó 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.ab.2005.01.009
2 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8

atomic absorption spectrometry (FAAS). However, rel- ment enhances the number of neutral atoms, thereby
ative to the latter technique, flameless AAS has some increasing the sensitivity. In the STAT system, a dou-
disadvantages such as its high cost, slowness, and great- ble-slotted quartz tube with the length of the upper slot
er proneness to interferences [6]. Although effective shorter than that of the lower slot is installed above the
chemical modifiers, background correction systems, im- burner and placed into the flame gases and analyte
proved furnace and platform designs, and careful opti- atoms using a pneumatic nebulizer system. The optimi-
mization of temperature programs were used to zation of the slotted tube using various designs and
remove the interferences [7], it is still widely studied in parameters, such as exit holes, tube length, and tube
relation to the interferences in this field of flameless materials, was reviewed in detail [9]. In that review, it
AAS [8]. On the other hand, it is recognized that because was also reported that the achieved improvements in
FAAS is faster, is cheaper, and does not require expert the sensitivity were in the range of 2- to 5-fold. To our
operators, it should be preferred to flameless AAS if knowledge, changes in the diameter and the upper slot
both of these methods can be used. Therefore, there length of tubes to improve the sensitivity of the
are continuing efforts to enhance the sensitivity of STAT–FAAS method have not been examined previ-
FAAS despite its being the mature analytical (many be- ously. In another study, 3-fold improvement in sensitiv-
lieve ‘‘over the hill’’) technique. The sensitivity of FAAS ity of Cu was achieved by using a tube having a diameter
is limited by several factors. The analyte atoms gener- of 6.0 mm, an upper slot length of 2.3 cm, a tube length
ated in the flame pass rapidly and continuously through of 12 cm, and a lower slot length of 5 cm [14].
the measurement zone during sample aspiration. A fur- In our previous studies [15–19], Cd, Pb, and Cu con-
ther limitation is the poor efficiency of the nebulizer/ centrations in biological and environmental samples,
burner system. A maximum of 10% of the aspirated such as human urine, fruits, milk, baby foods, soil,
sample solution reaches the flame. The sensitivity can and water, were determined by using an enrichment
be improved if the atomic vapor has been constrained method containing adsorption on activated carbon
to remain in the light path for a long time. In a review and/or the FAAS–STAT method. In these studies,
article, Matusiewicz recently discussed in detail the tech- 2.5- and 5-fold improvements in the sensitivity of
niques examined for this purpose [9]. Among these FAAS were achieved for Pb and Cd using the STAT
methods, the atom-trapping technique is designed in having a diameter of 8 mm and an upper slot of 4 cm,
two different shapes: the slotted quartz tube and the respectively.
water-cooled silica tube. Although these techniques were In the current study, unlike the previous studies, the
first described 25 years ago [10], it is evident that the sci- length of the upper slot and the diameter of quartz tube
entific literature on this topic has increased recently [9]. in the STAT were changed to improve the sensitivity of
The water-cooled silica system, in addition to having the FAAS. The obtained best conditions were applied to the
advantage of being more sensitive to improvement than determinations of Cd and Pb concentrations in the can-
the slotted quartz tube, has the disadvantage of needing cerous (malign) and noncancerous (benign) human thy-
a very large volume of a sample due to the longer aspi- roid tissues.
ration times—as long as 2 min for one measurement
[11–13].
Keeping atoms in the optical path with the so-called Materials and methods
slotted tube atom trap (STAT) system, as illustrated in
Fig. 1, has been found to be more popular recently. Be- Apparatus and reagents
cause quartz has a sufficiently high melting point and a
low thermal expansion coefficient, it has been chosen as An ATI UNICAM 929 model flame atomic absorp-
the material for the atom trap. The sensitivity improve- tion spectrophotometer equipped with ATI UNICAM
ment is attributed to the increased residence time of the hollow cathode lamps was used for the metal determina-
analyte atoms in the light path due to slower flame tions. The acetylene–air flame in FAAS in which the
speed. Furthermore, the more stable chemical environ- optimal conditions were studied is provided in the man-
ufacturerÕs instructions for the spectrophotometer. A
domestic microwave oven (Kenwood) was used for the
digestion of the tissues. The STAT was used to improve
the sensitivity of FAAS.
Unless stated otherwise, all chemicals used were of
analytical reagent grade. During all analytical work,
double-distilled water was used. All glass apparati were
kept permanently full of 1 mol L
1 nitric acid when not
in use. In the digestion procedures, concentrated nitric
Fig. 1. Schematic diagram of the STAT. acid (65%, Merck) and H2O2 (35%, Merck) were used.
 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8 3

Stock solutions of the metals (1000 mg L
1) were pre- 1. Begin with 0.75 g of the wet thyroid tissue.
pared by dissolving their nitrate salts in 1.0 mol L
1 ni- 2. Add 2.0 ml of HNO3/H2O2 (2:1) mixture.
tric acid. 3. Put into water bath for 30 min at 70 °C, stirring
occasionally.
Changes made on the STAT 4. Add 2.0 ml of the same acid mixture.
5. Put into Teflon bomb and place in the microwave
Various changes made on quartz tubes were studied oven.
to enhance the sensitivity. These changes included the 6. Irradiate at 450 W for 6.0 min and then cool.
length of the upper slot, the length of the diameter, 7. Add 1.5 ml of 0.1 mol L
1 HNO3.
and the length of the tube. Among the other suspected 8. Transfer into Pyrex tube.
factors, lower slot length depends on the slot of the bur- 9. After centrifugation, measure by STAT–FAAS.
ner. Hence, it is obvious that the change in its length has
not improved the sensitivity. The height of the tube over The blank digests were carried out in the same way.
the burner was always adjusted to obtain a maximum
absorbance. The studied quartz tube can be used only
in the flame of the acetylene–air mixture. The changes Results and discussion
made to the quartz tubes are given in Table 1. In all de-
signs, the length of the lower slot is 50 mm. It is known that the enhancement in the sensitivity of
FAAS is critically dependent on the flow rate of the
Preparation of tissue samples aspirated solution. In this study, the rate of the aspirated
solution was measured as 1 ml per 11 s. Table 1 shows
The samples were obtained in the formaldehyde solu- the obtained results for various designs of quartz tube
tion from private pathology laboratories and the pathol- together with the applied changes. The observed
ogy laboratories at Firat University in Elazig, Turkey. improvements in the sensitivity can be summarized as
Of these, 5 samples of cancerous (malignant) thyroid follows.
and 13 samples of noncancerous (adenoma) thyroid The effect of parameters, such as diameter of the tube,
were taken from patients of different sexes, ages, and liv- length of the upper slot, and length of the tube, on the
ing conditions except for 1 sample. The wet tissue sam- improvement in sensitivity was examined. Figs. 2 and
ples were cut into small pieces with a stainless-steel knife 3 were obtained from the data given for Pb in Table 1.
and were transferred into beakers. As can be seen, the sensitivity enhancement is dependent
on the tube diameter decreasing to the value of 5.0 cm
Digestion by using a microwave oven for Pb. Moreover, the sensitivity enhancement is depen-
dent on the length of the upper slot being greater than
The optimal parameters in the microwave oven, such the diameter of the tube. The obtained calibration
as power, time of radiation, and amount and species of graphs for Pb by using variously designed tubes are gi-
digestion reagents, were described elsewhere [14]. For ven in Figs. 4 and 5, and the calibration curves were
this purpose, the following steps were followed:

Table 1
Obtained improvements in the sensitivity of Pb and Cd by using the
STAT–FAAS method
Diameter of Length of upper Length of Increase in Increase in
tube (mm) slot (cm) tube (cm) Pb (fold) Cd (fold)
8 4.0 12 2.5 5.0
7 4.0 12 3.7 5.4
7 4.0 10 4.0 5.6
7 3.0 10 4.5 7.0
7 3.0 12 4.2 6.7
7 2.8 12 4.6 7.6
6 3.0 12 4.7 7.7
6 2.8 12 5.0 8.7
6 2.3 12 6.0 10.0
5 2.3 12 6.0 10.0
Limit of quantitation with direct FAAS 200.0 40.0
(ng ml
1)
Fig. 2. Sensitivity enhancements dependent on the changes in diameter
Note. The length of the lower slot is 5 cm. of the tube using different lengths of the upper slot for Pb.
4 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8

Fig. 5. Calibration graphs for Pb. Variations in the sensitivity are related
to the tube diameter and the length of the upper slot. *, Length of the tube
diameter in millimeters (and length of the upper slot in centimeters).

Fig. 3. Sensitivity enhancements dependent on the changes in length of

the upper slot using different diameter lengths of the tube for Pb. From the data given for Cd in Table 1, Figs. 6 and 7
were obtained. As can be seen, the sensitivity is en-
hanced with the tube diameter decreasing to the value
found to be linear in the given ranges. The equations for of 5.0 cm for Cd. In addition, the sensitivity enhance-
the calibration curves for Pb without the STAT and with ment dependent on the length of the upper slot being
the most sensitive STAT are as follows: greater than the diameter of the tube, similar to the case
y ¼ 0:0466x þ 0:4085; of Pb. The calibration graphs for Cd obtained using var-
iously designed tubes are given in Figs. 8 and 9, and the
R2 ¼ 0:9996; calibration curves were found to be linear in the given
for Pb without the STATð100–800 ng ml
1 Þ ranges. The equations for the calibration curves for Cd
without the STAT and with the most sensitive STAT
y ¼ 0:2794x þ 2:2026; are as follows:
R2 ¼ 0:9999; y ¼ 0:25x;

1
for Pb with the most sensitive STATð100–800 ng ml Þ R2 ¼ 1:0000;
for Cd without the STATð40–100 ng ml
1 Þ

Fig. 4. Calibration graphs for Pb. Variations in the sensitivity are

related to the tube diameter and the length of the upper slot. *, Length
of the tube diameter in millimeters (and length of the upper slot in Fig. 6. Sensitivity enhancements dependent on the changes in diameter
centimeters). of the tube using different lengths of the upper slot for Cd.
 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8 5

Fig. 9. Calibration graphs for Cd. Variations in the sensitivity are

related to the tube diameter and the length of the upper slot. *, Length
of the tube diameter in millimeters (and length of the upper slot in
centimeters).
Fig. 7. The sensitivity enhancements depending on the changes in
length of the upper slot using different diameter lengths of tubes for Cd.
The main advantages of the STAT–FAAS method, in
comparison with conventional FAAS, lie in the in-
creased sensitivity and in the reduction of potential
interferences because the former technique allows great-
er dilution of the sample. Devitrification of the slotted
quartz tube was prevented by aspirating a 1% (m/v) lan-
thanum solution. As a result, the service life of the
quartz tube was increased. On the other hand, it was ob-
served that the service life of the quartz tube was related
to the wall thickness of the tube. Measurements of more
than 100 cycles can be done using a tube having a wall
thickness of 1.5 mm.

Sensitivity and precision

Levels of Pb and Cd in the reagent blanks in the total

analytical steps were found to be 8.0 and 0.5 ng ml
1
Fig. 8. Calibration graphs for Cd. Variations in the sensitivity are with standard deviations of 1.0 and 0.1, respectively.
related to the tube diameter and the length of the upper slot. *, Length Therefore, the detection limits for Pb and Cd, defined
of the tube diameter in millimeters (and length of the upper slot in as three times the s values of blanks, were calculated
centimeters). as 3.0 and 0.3 ng ml
1, respectively. For the total analyt-
ical procedure containing the digestion procedure, the
y ¼ 2:4972x þ 1:12; relative standard deviations measured for concentra-
R2 ¼ 0:9999; tions of 100 and 20 ng ml
1 of Pb and Cd were found
to be 5 and 3%, respectively (n = 7).
for Cd with the most sensitive STATð4–100 ng ml
1 Þ
As can be seen from Table 1, the sensitivity is not im- Accuracy and interferences
proved much when the tube has a diameter of less than
6 mm for both Pb and Cd. This result may be related to The accuracy of the method was studied by examin-
the diameter of the light path, which is larger than ing the certified reference material containing skim milk
5 mm, particularly in the entrance to the tube. As a re- powder (BCR 151) and standard reference material (to-
sult, determinations of Pb and Cd concentrations as mato leaves–1573a). The results are given in Table 2. It
low as 35 and 4 lg L
1, respectively, were achieved by can be seen that the recovery values for BCR 151 were
the modified STAT–FAAS method, in which the tube found to be 100% for Pb and 96% for Cd. The recovery
had a length of the upper slot of 2.3 cm and a diameter value for Cd in tomato leaves–1573a was found to be
of 6 mm. 98%.
6 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8

Table 2
Pb and Cd concentrations in cancerous and noncancerous (adenoma) thyroid tissues
Thyroid tissue Pb (ng/g) Cd (ng/g)
Cancerous Noncancerous Cancerous Noncancerous
Literature value [23,25] 17.8 ± 1.9 mg/kg, freeze-dried basis 11.6 ± 1.2 mg/kg, freeze-dried basis <0.1–31.75 mg/kg,normaltissue
1 250 ± 35 150 ± 17 110 ± 10 153 ± 12
2 170 ± 25 145 ± 17 140 ± 20 172 ± 2
3 160 ± 20 110 ± 20 120 ± 13 208 ± 12
4 190 ± 21 100 ± 13 95 ± 12 97 ± 21
5 140 ± 15 163 ± 19
6 50 ± 8 700 ± 51
7 <50 450 ± 42
8 <50 105 ± 15
9 110 ± 15 150 ± 21
10 75 ± 11 95 ± 11
11 120 ± 17 105 ± 14
12 140 ± 17 302 ± 40
13a 185 ± 20 160 ± 18 72 ± 11 128 ± 22
Mean 191 ± 35 118 ± 34 107 ± 26 218 ± 176
138 ± 38b
P = 0.0026 P = 0.048b
BCR 151 certified 2002 ± 26 101.0 ± 8.0
BCR 151 found 2000 ± 21 97 ± 7
Tomato leaves–1573a certified — 1520 ± 40
Tomato leaves–1573a found — 1493 ± 26
Note. Results are on a fresh weight basis (n = 3). Cancerous and noncancerous tissues belong to different persons (with one exception).
a
The results in this line belong to the same person.
b
Except for the values of 302, 700, and 450 for Cd.

In addition, the thyroid samples containing the high-

est concentrations of Pb and/or Cd were analyzed by
using both direct conventional FAAS and the STAT–
FAAS method. The obtained results using the STAT–
FAAS method were compared with those using direct
conventional FAAS. It was observed that the results ob-
tained using the STAT–FAAS method were in agree-
ment with those obtained using conventional FAAS
(>97%). In addition, the recoveries of Pb and Cd from
the thyroid samples fortified with the Pb and Cd were
used to test the accuracy of the modified method. The
concentrations of Pb and Cd spiked to the samples were
in the ranges of 100–300 and 10–30 ng ml
1, respec-
tively. It was found that at least 95% of the Pb and
Cd added to the thyroid samples was recovered. The ef-
Fig. 10. Calibration and standard addition graphs for Pb in thyroid
fect of contamination was eliminated by subtracting the sample.
obtained values for blanks. In addition, to overcome the
enhancement or suppression due to the presence of ma-
jor components of the thyroid matrix, calibration solu- the determination of Pb and Cd in human thyroid tis-
tions were performed within the sample matrix itself. sues using a quartz tube having an upper slot length
On the other hand, the standard additions method for of 2.3 cm and a diameter of 6 mm.
the determination of Pb and Cd in the thyroid samples
was examined. The slopes of the calibration curves were Determination of Pb and Cd in human thyroid tissues
compared with the slopes obtained using the standard
additions method (Figs. 10 and 11). These results indi- It was reported in the literature that trace element
cate the absence of chemical interferences given that concentrations of healthy adult thyroid glands were
the slopes of calibration curves and standard additions independent of sex and age [20]. The International
are identical for both Pb and Cd. Therefore, the calibra- Agency for Research on Cancer (IARC) lists inorganic
tion graphs were used to determine Pb and Cd in the Pb compounds as possible human carcinogens, based
thyroid samples. The optimized method was applied to primarily on data from rodents [21]. However, human
 Improvement of sensitivity in lead and cadmium determinations / M. Yaman / Anal. Biochem. 339 (2005) 1–8 7

dry weight basis by using a water content of 74.2% in

thyroid. In fact, Katoh and coworkers also reported that
Cd values were higher by a factor of 4.51 in comparison
with other values found in the literature [26].

Conclusions

The proposed method has some advantages such

as high speed, less risk of contamination, low cost,
and easy manufacturing of the required quartz tube.
Although the achieved improvement is modest (6-
and 10-fold for Pb and Cd, respectively), the modi-
fied method has great importance in comparison with
other enrichment techniques, such as adsorption and
extraction, due to its simplicity and instant
Fig. 11. Calibration and standard addition graphs for Cd in thyroid applicability.
sample. Finally, the sensitivity between the flame and furnace
atomization for some elements, such as Pb and Cd, is
bridged gradually via the atom trap in flame. In this
epidemiological studies have revealed little evidence of a study, the sensitivity improvement, which had not been
carcinogenic risk for even quite heavy exposure to Pb obtained by the STAT previously, was achieved for Pb
compounds [22]. On the other hand, a finding of clear and Cd by using very simple modifications of the STAT
differences between the element concentrations of be- method. The limits of quantitation were found to be 35
nign and malign thyroids has great importance given and 4 ng ml
1 for Pb and Cd, respectively. The required
that this result can be applied diagnostically. volume of sample for this method is less than that for
Reddy and coworkers, using the X-ray emission other enrichment methods; only 0.6 ml of solution is re-
method, found Pb concentrations of cancerous thyroid quired for two metal determinations.
to be higher than those of adenoma thyroid [23]. The re-
sults of the current study also showed that there was an
increase (P < 0.005) in the Pb concentrations of cancer-
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