Professional Documents
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DOI 10.1007/s10967-012-1876-x
123
144 S. Waheed et al.
In Pakistan geophagy of multani mitti (MM) clay is very traceability of the results. The same RMs were also used as
common especially amongst the women folk and children. multi-elemental standards for quantification of toxic ele-
People generally use raw MM clay for oral ingestion, as ments in the sample using INAA. Approximately 100 mg
medication, in aesthetic medicine and as body and hair of MM samples in triplicate along with IAEA RMs were
wash. Although therapeutic properties of clays have gained packed and sealed in polyethylene capsules. Taking into
especial attention, it is its toxic contaminants that require consideration the elements to be quantified different suites
scrutiny. It is believed that people who are habitual con- of samples were prepared and packed in reactor rabbits. All
sumers of unprocessed clay may be at risk for several irradiations of these targets were performed adjacent to the
significant health problems due to intake of toxic elements reactor core of the 27 kW tank-in-pool type miniature
over long period of time [6]. Moreover any material to be neutron source reactor. The thermal neutron flux density at
consumed orally or as medication as in pharmaceuticals this site was 1 9 1012 cm-2 s-1. All samples after desired
must not be toxic or have severe side effects. The presence cooling were transferred to pre-cleaned and pre-weighed
of these elements even in minute concentrations can be a polyethylene counting capsules for analysis.
potential threat to the consumer or patient [4]. It is there- High purity germanium detector (Canberra Model AL-
fore necessary to asses its quality through accurate and 30) coupled to a PC-based Intertechnique Pro-286e Mul-
precise characterization of the toxic element contents to tichannel Analyzer (MCA) was used for quantification of
identify varieties of clays which are suitable for direct MM samples in accordance with the optimized radio-assay
consumption. scheme. The system resolution was 1.9 keV at 1332.5 keV
Characterization of toxic elements in MM is imperative peak of 60Co with peak to Compton ratio of 40:1. ‘‘Inter-
to establish baseline of these elements for nutritional gamma, version 5.03’’ software was used for obtaining all
safety. In this study toxic elements have been quantified in spectra. An indigenous computer program was used for the
MM clay using instrumental neutron activation analysis calculations and statistical data treatments [7].
(INAA) together with atomic absorption spectrometry
(AAS). As children and pregnant women are at greater risk AAS methodology
of exposure to toxic elements due to ingestion of MM clay,
this work takes into consideration the intake of MM clay in Approximately 1 g of MM clay sample was taken in
these subjects along with men, women and lactating 100 ml digestion flask with air condenser (30 cm long)
women. attached to it and 10 ml of aqua regia was added to it. For
analysis of soil and clay samples instead of total digestion
usually pseudo total digestion is performed with boiling
Experimental aqua regia under reflux. The contents were heated on a hot
plate at 85 °C for leaching for 2h. After cooling, drop wise
Sampling and sample preparation 1.5 ml of H2O2 was added at 60 °C until completion of
reaction [8]. The leachate was filtered and solution was
MM clay reserves are located 45 km North West of Dera made up to 10 ml in a volumetric flask with de-ionized
Ghazi Khan District in Pakistan. The samples were collected water. The digested samples were analyzed in triplicate.
in clean plastic bags from this site and brought to the Paki- The applied procedure was validated by simultaneous
stan Institute of Nuclear Science and Technology (PINS- processing and analysis of IAEA S-7 and IAEA SD-M-2/
TECH) in Islamabad where sample preparation and analyses TM RMs for Cd and Pb. Quantification of Cd, and Pb, was
were performed. Sample processing and preparation was carried out using a Hitachi model Z-2000 Polarized Zee-
done in a laminar flow fume hood. The samples were cru- man Atomic Absorption Spectrometer (AAS) coupled with
shed and sieved to obtain homogenized powder with particle software based data handling facility.
size of \0.125 mm. The processed samples were stored in
pre-cleaned polyethylene bottles. The homogeneity of the
prepared MM material was checked through analysis of Mn Results and discussion
contents in 100 mg samples. The measurement variation
was found to be \6 % around the mean values confirming MM clay has been studied for its toxic elemental content
the homogeneity of the preparation. using INAA and AAS techniques. For the quantification of
As, Br, Hg and Sb by INAA, two radio-assay protocols
INAA methodology presented in Table 1 were employed. In the first scheme the
targets were irradiated for 1h and after subsequent cooling
Two IAEA reference materials (RMs) (IAEA soil S-7 and for 1–2 days 76As, 82Br and 122Sb were determined. The
IAEA Marine sediment SD-M-2/TM) were used to ensure second scheme quantified 203Hg where the sample was
123
Toxic element composition of multani mitti clay 145
Table 2 Quality assurance data for IAEA matrix RMs (values expressed in lg g-1 unless otherwise specified)
Element IAEA S-7 IAEA SD-M-2/TM
Certified value 95 % CI Our value ± Unc. Certified value 95 % CI Our value ± Unc.
Table 3 Global comparison of MM clay with other reported clays (values expressed in lg g-1 unless other wise specified)
Clays As Br Cd Hg Pb Sb
MM Clay 2.46 ± 0.16 2.93 ± 0.25 0.101 ± 0.015 0.137 ± 0.017 8.30 ± 0.30 0.423 ± 0.050
WC38 0.6–4.1 1.5–3.0 – – – 0.32–1.90
38
GC 4.1–8.9 0.5–3.3 – 0.031–0.048 – 0.48–1.06
SW-y-2 (SC)39 – – – – 20.63 ± 3.14 0.436 ± 0.076
RC40 14.6 ± 0.6 – – – – 1.39 ± 0.19
NIST-SRM 679 (BC)40 9.7 ± 0.4 – – – – 1.0 ± 0.1
MC41 11.8–26.7 – 0.110–0.250 0.012–0.021 19.2–32.9 52.0–97.1
15
Sikor (BC) 3.8–13.1 – 0.09–0.40 – 21–26.7 –
irradiated for 5 h followed by 2–3 weeks of cooling time. to the fact that Cd in IAEA S-7 is not certified while in
The observed elemental interferences were handled as IAEA SD-M-2/TM the certified concentration of this ele-
mentioned in our earlier works [9, 10]. Cd and Pb in MM ment is low with large reported error. Hg quantified by
samples were determined using AAS. INAA also shows lower precision as in IAEA S-7 only
The quality assurance of the elemental analysis was information value is reported for this element. Moreover
ascertained by comparison of the results of two control high variation coefficient (mc) of Hg in both standards
material, IAEA S-7 and IAEA SD-M-2/TM obtained using could be due to its low concentration and low count rate for
INAA and AAS with the certified data. The accuracy of both standards.
results helps to ensure the trueness and bias of the adopted Toxic elements quantified in MM clay using INAA and
methodology in accordance with ISO-5725 standards [11]. AAS are presented in Table 3. The concentrations of all
Table 2 shows good agreement between the IAEA certified elements (As, Br, Cd, Hg, Pb and Sb) are reported on dry
values and results obtained in the current study using weight basis and are the averages of several determina-
INAA and AAS. The overall precision for the measurement tions. INAA of MM clay shows good precision for As and
of all elements when analyzed through paired difference Br with mc \ 10 % around the mean values. However for
test at 95 % confidence level was found to be acceptable Hg and Sb relatively high mc [ 10 % is observed. Con-
and in range of these RMs [12, 13]. Relatively high error centration of Pb determined by AAS shows very good
was observed for Cd measured by AAS which may be due precision with mc \ 5 % while for Cd mc is high (14.8 %).
123
146 S. Waheed et al.
The composition of toxic elements in MM is quantified in (MML) and children of ages 4–8 (MMC1) and 9–13
the descending order; Pb [ Br [ As [ Sb [ Hg [ Cd (MMC2) with respective estimated body weights of 70, 55,
where all measured toxic elements are present in trace 65, 60, 20 and 40 kg. Weekly contribution to PTWI value,
amounts. in which the percentage numbers are showed as the ratio of
Comparison of our results for toxic elements in MM the intakes by geophagy of the MM clay to the PTWI
clay has been made with other clays. Table 3 presents values for each subject groups are presented in Table 4.
results on these elements from Brazilian white and green The weekly intakes of characterized elements have been
clays (GC) used for pharmaceuticals and cosmetics, SW-y- calculated on the basis of domestic survey with fixed
2 Na rich bentonite from Wyoming, Ohio red clay (RC), amount of MM clay ingested by each category.
NIST-SRM 679-brick clay, Muddy clay (MC) from eastern
Gulf of Finland and Sikor-backed clay from Bangladesh Arsenic (As)
[14–17]. Assessment of this data shows that As
(2.46 lg g-1), Cd (0.101 lg g-1), and Pb (8.30 lg g-1), As is ubiquitous in our environment and is a poison in large
are lowest in MM while its Br (2.93 lg g-1), and Hg amounts. It is the third most prevalent element in the
(0.137 lg g-1) content are high. However As in MM clay earth’s crust. As has been declared as a human carcinogen
falls in the range cited for white clays (WC). RC and MC by the International Agency for Research on Cancer
contain very high levels of As with respective concentra- (IARC) since 1980 [20]. Excessive exposure to this ele-
tions of 14.6 and 11.8 lg g-1. Cd levels in MC are com- ment poses health problems such as various types of can-
parable to MM Clay and Sikor (BC) has relatively high cer, cardiovascular diseases, diabetes and neurological
concentration of this element. Pb content in SW-y-2 (SC), disorders as well as dermal effects [20]. According to the
MC, and BC (20.6, 19.2, and 23.2 lg g-1 respectively) are National Research Council excessive As intake may pose
comparable and almost twice the levels of MM clay. Br greater risk for both cancer and non-cancer effects in
levels in some of the GC are the lowest with a range of infants and children. Numerous other disorders are linked
0.5–3.3 lg g-1 and therefore Br levels in MM clay and to this element including respiratory problems, nervous
WC fall in this range. Hg with range of 0.12–0.021 lg g-1 system effects, low IQ and reproductive effects. Pregnancy
and Sb with range of 0.20–0.57 in MC are the lowest. complications have also been related to As intake such as
Concentration of Sb in MM (0.423 lg g-1), GC fetus abnormalities, abortions, stillbirths, premature deliv-
0.48 lg g-1) and SC (0.436 lg g-1) are comparable while eries and reduced birth weight of babies. Even low level
its value in RC (1.38 lg g-1) and BC (1.0 lg g-1) is high. As-exposures have been reported to affect human health
On the whole the composition of MM clay is close to especially in malnourished people [21]. Trace amounts of
Bangladeshi sikor (BC). The variation in elemental con- As were quantified in MM clay with concentration of
centrations in different clays may be attributed to differ- 2.46 lg g-1. The calculated intake values for As in MMM,
ences in mineralogy, depth of the sample site, geographic MMW, MMP, MML, MMC1 and MMC2 presented in
location and its age. Comparison of clays shows that MM Table 4 are 36.9, 73.8, 172, 123, 12.3 and 24.6 lg
clay contains low levels of As, Cd, Pb and Sb while it’s Br respectively. Figure 1 shows that intake of As by each
and Hg levels are higher. category of MM consumer contributes to about 3.6, 9.1, 18,
As toxic elements are reported to accumulate in the 13.9, 4.2 and 4.2 % of the recommended PTWI values
body, the relevance of these elements in MM clay through which is equivalent to 14.7 lg kg-1 body weight per week
dietary intake has also been evaluated and compared with [18, 22]. The estimated dietary exposures of As through
the provisional tolerable weekly intakes (PTWI) set by the intake of MM clay for all the population groups studied are
Joint FAO/WHO Expert Committee on food additives well below the PTWI and are unlikely to constitute a risk to
(JECFA) [18]. It was important to compare our values with health. However pregnant and lactating women should be
PTWI as in this way regular ingestion of MM clay can be careful in consuming large amounts of MM clay.
scrutinized for its consumption over a long period of time
without appreciable health risk. Geophagy of MM is more Bromine (Br)
popular in children and women, especially in pregnant and
lactating women. It is reported that most of the toxic ele- Bromine is naturally present at very low levels in food
ments in pregnant and lactating women can transfer from articles. Elemental bromine is toxic Once ingested it is very
the mother to the fetus and through milk to newborn slowly excreted from the body causing conditions of
placing the health of the unborns and newly born baby at intoxication called bromism with adverse health effects.
risk [19]. Considering this fact, PTWI values have been This state is characterized by neurological, psychiatric,
used to estimate its values for men (MMM), women dermatological, delirium, psychomotor retardation schizo-
(MMW), pregnant women (MMP), lactating women phrenia and possibly endocrine effects [23]. Consuming
123
Toxic element composition of multani mitti clay 147
contribution
to PTWI
Weekly
0.361
0.252
value
4.18
0.01
2.13
–
10 g week-1
bw = 40
MMC2
24.6
29.3
1.01
1.37
83.0
4.23
contribution
to PTWI
Weekly
0.361
0.252
value
4.18
0.01
2.13
–
5 g week-1
Table 4 Weekly intake of toxic elements through consumption of MM clay in Pakistan (All intakes expressed in lg per week unless specified)
bw = 20
MMC1
12.3
14.7
0.51
0.69
41.5
2.12
Fig. 1 Comparison of weekly As intake through ingestion of MM by
different subjects with respective PTWI values
contribution
to PTWI
Weekly
0.839
value
13.9
1.20
7.09
5.05
6.85
21.2
123
147
415
1.08
value
intakes of 44.0, 87.9, 205, 147, 14.7 and 29.3 lg were cal-
culated for MMM, MMW, MMP, MML, MMC1 and
70 g week-1
7.07
9.59
29.6
172
205
581
0.549
value
9.13
4.64
this clay is safe from nutritional safety point of view for all
30 g week-1
types of consumers.
bw = 55
MMW
73.8
87.9
3.03
4.11
12.7
249
Cadmium (Cd)
contribution
0.009
0.309
0.216
3.59
1.82
6.35
125
7,000
14.7
7.00
1.61
25.2
42.0
Hg
Cd
As
Pb
Sb
Br
123
148 S. Waheed et al.
Mercury (Hg)
123
Toxic element composition of multani mitti clay 149
Lead (Pb)
123
150 S. Waheed et al.
therefore recommended that regular monitoring of blood 22. Zhang HH, Yuan HX, Hu YG, Wu ZF, Zhu LA, Zhu L, Li FB, LI
Pb levels of all MM clay consumers be carried out on a DQ (2006) China Environ Pollut 144:492–499
23. Waheed S, Rahman S, Gill KP (2009) J Radioanal Nucl Chem
regular basis to check for their dietary exposures to lead. 279:725
24. Pavelka S (2004) Physiol Res 53:S81
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