Intake of Lead, Cadmium and Mercury in Kaolin-eating: A Quality Assessment
Clay-eating or kaolin-eating (geophagy or geophagia) is a global practice that exists among humans as well as numerous animal species. Geophagy has been studied by anthropologists, geologists, nutritionists and ecologists in present and traditional cultures from areas across continents, including present-day Arizona and California, Central and South America, Sweden and Sardinia, sub-Saharan Africa, Indonesia and Australia. In 2002, the European Union alerted the Cameroon Ministry of Public Health that kaolin carried from Cameroon to Europe had abnormally high amount of lead (Pb) at levels a 100 times higher than the maximum permissible level. This kaolin that is sold on the several markets is mined from different sources, some locally and others from Nigeria. To investigate this, markets of wholesale dealers in kaolin were visited in five districts selected in a manner as to represent the entire territory. Six samples of 1 kg each were then randomly selected and bought. A total of 30 kg was collected from all the districts. The sources of procurement were also visited and 24 samples of approximately 300 g each were collected from all the harvesting sites. Analytical methods for flame spectroscopy were used and statgraphic for data analysis. The results show that all kaolin is contaminated not only with Pb but Cd and Hg as well. The differences in Pb content at district levels is statistically significant p = 0.02 (p<0.05) while no significant difference exist as regards the origin of kaolin or source of procurement (p = 0.53).
August 21, 2011; Accepted: November 14, 2011;
Published: December 17, 2011
The eating of clays or kaolin occurs among cultural groups on every inhabited
continent. Geophagy is prevalent in Asia, the Middle East, parts of Latin America
and in the rural South of the United States. In Sub-Saharan Africa hundreds
of cultures including both farmers and nomads consume dirt, mainly clay (kaolin)
but in some cases sand. Clay consumption is nearly everywhere most common among
pregnant women, perhaps because of its antinausea effects, experts hypothesize.
The limited data indicate that from 30% to 50% of pregnant women in large areas
of Africa and among rural blacks in parts of the American South consume clay
and that hundreds of millions of women worldwide do it during pregnancy (Vermeer
and Ferrell, 1985).
Kaolin is a broad name given to a range of clay-compound substances made up
of Kaolinite (predominately) and several other minerals produced by the alteration
of felspathic rock. As a compound, the composition of Kaolinite and other minerals
and substances varies from sample to sample. Depending on its chemical composition
it presents as white, green, pink, grey, yellow or red in colour and has a soft
plastic nature. Like all other clay it is a hydrated silicate that is very stable
during natural conditions. It is ranked as one of the top seven industrial minerals
in the world (DME, 2005). Depending on its individual
chemical characteristics and the extent to which it is processed, Kaolin is
used as filler and input in the manufacture and production of several goods
including: Ceramics, bricks, tiles, pottery, cement, paper, fibre glass, refractories,
plastic, pharmaceutics, mineral wool, cosmetics, paint, rubber, industrial products,
light bulbs, food additives, toothpaste etc. (DME, 2005).
Physiologically, some nutritionists and other observers have tended to view geophagia
and pica in general as a compulsive craving and as a medicine to alleviate discomfort
in some respects. Kaolin or clay could absorb dietary toxins and bacterial toxins
associated with gastro-intestinal disturbance (Walker et
al., 1997). The presence of aluminium, magnesium and benzoic groups has
made Kaolin to possess antacid properties and can be a therapeutic food for people
suffering from gastric upsets or ulcers. Further, because of its covering properties,
it has a bandaging role in gastro-enterology (Banenzoue, 1992).
In a hot and humid milieu, kaolin develops negative charges between its layers
and will attract positive charges (such as heavy metals) resulting to contamination
(Gamiz et al., 1988). Lead, a naturally occurring
metal, has always been present in soils, surface waters and ground waters. Lead
content of agricultural soils ranges from >1 to 135 mg kg-1 with
a median value of 11 mg kg-1 (Holmgren et
al., 1993) and will certainly through leaching or washing by rain reach
kaolin deposits especially those deposits that are along or within streams/rivers
or on slopes below cultivated farm fields. The situation is more serious when
the stream/river that is reaching kaolin deposits has passed through a city
or industry (Nweke et al., 2008; Danazumi
and Bichi, 2010). Inner-city neighbourhoods in most of our major cities
have mean or median soil Pb concentrations in excess of 1000 mg kg-1
(Angle et al., 1974; Johnson
et al., 1975; Bornschein, 1986; Mielke
et al., 1989; Madhaven et al., 1989;
Usman et al., 2007) with values as high as 50,000
mg kg-1 being reported (Chaney et al.,
1989). Most of these elevated lead concentrations observed in the urban
soils are assumed to come from various anthropogenic sources: Industrial emissions,
vehicular emissions and exterior lead paint (EDF, 1990;
Madukosiri and Dressman, 2010). Additionally, lead is
also added to soil as the insecticide lead arsenate, impurity in fertilizers
as well as from mining and smelting activities (Davies, 1990).
In 1999, the German authorities came out with information of the presence of
dioxin in some portions of kaolin (clay) from mines of the Westerwald region
that was used to improve flow during pumping when moving the animal feed from
one store to another. This came to add to the medical fear that extreme overindulgence
in clay eating can block the colon, which can lead to perforation of the colon
and death. A more common problem is the geophagic syndrome seen over the last
three decades among scores of clay eaters in Portugal, Iran, Turkey, Egypt and
other Middle Eastern countries. The syndrome involves anemia and zinc deficiencies
(Virginia et al., 1968; Hooda
et al., 2002), growth retardation, delayed sexual maturity and liver
and spleen enlargement (Danford and Huber, 1982). Also,
In 2002, the European Union alerted the Cameroon Ministry of Public Health that
kaolin carried from Cameroon to Europe had abnormally high amount of lead (Pb)
at levels a 100 times higher than the maximum permissible level. In 2003, the
national Ministry of Public Health then prohibited the consumption of kaolin
within the confines of its jurisdiction. This ban has not stop kaolin dealers
from importing or exporting their product or industries from exploiting or using
kaolin as a raw material.
Lead is a poisonous metal that can damage nervous connections (especially in
young children) and cause blood and brain disorders. Lead poisoning typically
results from ingestion of food or water contaminated with lead; but may also
occur after accidental ingestion of contaminated soil, dust, or lead based paint
(ATSDR/DTEM, 2006). It is probable that lead poisoning
may also occur in the case of pica or geophagia which is deliberate ingestion
of earth or dirt since lead occurs naturally in them at levels above the required
threshold for edible matter. Heavy metal toxicity which is frequently the result
of long-term, low-level exposure to pollutants has often been investigated in
air, water, food and numerous consumer products (Eleni
et al., 2006; EPA, 2006) but hardly investigation
is carried out in the case of pica (or geophagia as in this case), or to check
the validity of industrial products with clay or kaolin as raw material.
Since, it is established that lead can contaminate kaolin it is important to
investigate and confirm or infirm the ministers assertion that kaolin
is toxic. The investigation has assumed that lead was associated with other
toxic heavy metals particularly cadmium and mercury. The latter together with
lead constitute the three most pollutant heavy metals (FAO/WHO,
1993) and as such contamination of kaolin could be attributed to all the
MATERIALS AND METHODS
A pilot study justifying the reason for the study was carried out in the Bamenda region (North Western Cameroon). An investigation was carried on a total of 40 consumers (32 women and 8 children) two months before we started with our market visits. Kaolin vendors gave information regarding the market situation of kaolin and consumption rate. Daily consumption was evaluated by asking consumers to state the amount of money in CFA they use in purchasing kaolin each day. Samples of kaolin were then purchased in varied amounts of money stipulated and weighed.
Sampling: We then visited the popular markets of Douala, Yaounde, Bafoussam, Bamenda, Ngaoundere and Limbe/Tiko (one market each for wholesale and retail was chosen in each district). In each market, we met wholesale dealers and asked for their sources of procurement and at the same time six samples of 1 kg each were randomly selected and paid for. A total of 30 kg carefully labelled and numbered was collected from all the sites. They were then carried to the laboratories where they were stored at ordinary temperature in waterproof papers. Kaolin harvesting sites that supply kaolin into the market (Balengoum and Mbengwi in Western and North Western Cameroon, respectively and one harvesting site in Nigeria) were revealed by wholesale dealers as their sources of procurement. They were subsequently visited to appreciate the sites and observe local conditioning. Four samples of approximately 300 g each were picked from four cardinal points (N, S, E and W) of each harvesting sites. Conditioning that varied from direct incubation at the harvesting sites (in Bangangté) via direct sun-drying and smoking of the blocks in basins, transforming them into a substance known locally as eko (in Nigeria) to simple sun drying or placing of kaolin above the fire sites (in Mbengwi) was observed. Four samples were then purchased after each kind of conditioning. A total of 24 samples were collected.
Reagents: Standard solutions of Lead (Pb), Cadmium (Cd) and Mercury (Hg) were prepared from stock solutions of 1000 μg L-1 (ppm) by following appropriate dilutions using 10% nitric acid. Glassware was cleaned by overnight soaking in HNO3:H2O (1:1) followed by repeated rinsing with water. Only de-ionized water was used throughout this work and acids were all of analytical grade.
Sample preparation and procedure: Samples were ground using a mortar
and sieve with the USA Standard Testing sieve N°120, opening in micrometer
125 (Tyler Equivalent 115Mesh). Mineralization was carried out in a humid medium.
About 1.0 g of the pulverized kaolin samples were digested for 30 min in a mixture
of hot perchloric acid (2 mL), nitric acid (10 mL) and sulphuric acid (2 mL)
(AOAC, 1984). This was filtered through acid washed filter
paper (Whatman 42) into 25 mL flask and made to mark with de-ionized water.
The contents were each transferred into 30 mL test tubes (decontaminated initially
by steeping in 10% nitric acid) The samples were thus ready for reading at the
atomic absorption spectrometer.
Atomic absorption spectrophotometer analysis of samples: The heavy metal
analysis was done using Perkin 311 model Atomic Absorption Spectrophotometer,
as described by Burtis and Ashwood (2001). From the stock
solution of each element containing 1000 parts per million (1000 ppm), four
different standard solutions were prepared. A blank was prepared using water
and acid mixture (perchloric, nitric and sulphuric acids) only. The blank was
first aspirated into the flame to give a reading of zero absorbance. Thereafter
each of the four standards was aspirated in-turn, starting from the solution
with the lowest concentration. Each standard gave an absorbance value that corresponded
to its concentration. With the standard curve the unknown concentration of the
particular cation in the sample was obtained. Air-acetylene gas was used as
fuel, while the following wavelengths were used for the cationic estimations-Lead
283.3 nm, cadmium 228.8 nm and mercury 253.65 nm (with special attention for
Hg; using nasal masks). The absorption signals were evaluated by subtracting
the value of blank from the signal of the sample.
Statistical analysis: All determinations were done in duplicates and statgraphic (Statgraphic 5.0) used for statistical analysis-the Duncan test used to compare the different dependent variables.
RESULTS AND DISCUSSION
A descriptive analysis of the questionnaire is as follows; Kaolin procurement included three sources; Mbengwi (2.5%), Bangante (15%) and Nigeria (82.5%). 62.5% of the vendors met in the market consumed kaolin while 37.5% were only vendors and never consumed kaolin. Vendors revealed that the rate of purchase of kaolin was high. At consumption level, the reasons for consumption varied from the appreciation of taste, flavour, to therapeutic or beliefs or simply no reasons at all. The health problem encountered mostly was constipation. Ninty percent of those who filled the questionnaire were aware of the ban passed by the Ministry of Public Health on kaolin consumption. 42.5% consumed kaolin in pregnancy, 35% could not remember while 22.5% never consumed kaolin in pregnancy. Estimated average consumption per day stood at 59.2±17.7 g.
These results reveal that kaolin is contaminated with Pb, Cd and Hg. The difference
between Pb contents at district levels (Table 1) is statistically
significant p = 0.02 (p<0.05) while no significant difference exist in Cd
and Hg (p = 0.22 and 0.5, respectively). Also, differences in Pb, Cd and Hg
contents as regards the origin (Nigeria, Bangante or Mbengwi) of kaolin (p =
0.53, 0.25 and 0.92, respectively) are statistically insignificant.
It is clear that heating during conditioning reduces a bit of Pb, Cd and Hg (Table 2) but the reduction is not statistically significant (p = 0.25, 0.33 and 0.91, respectively). Ranges illustrate that heavy metals are not evenly distributed at the harvesting sites and in kaolin samples (Table 1, 2). This could result from differential contamination from running rain water with varying concentrations of heavy metals due to human activities at the upstream of the harvesting sites or variation in leaching, or contamination by running rain waters or streams that are on and off during the rainy and dry season, respectively (-the case in Southern Nigeria near Onitsha, at Nteje, Achala-Agu village). Whatever the source of kaolin may be, the differences in the levels of Pb, Cd and Hg (p = 0.45, 0.74 and 0.79, respectively) are not statistically significant.
Since kaolin is directly consumed by human-following the pathway of food, exposure
to these heavy metals is oral and the exposure limits have been compared to
those of Food and Agricultural, FAO/WHO (1999) set at
0.2, 0.1 and 0.3 μg g-1 for Pb, Cd and Hg, respectively. This
thus indicates that kaolin in the market is contaminated only with Pb but also
with Cd and Hg.
Health risk and hazards of exposure: The possibility and the danger
of lead or heavy metals getting into human food chain through eating contaminated
clay (by birds, animals etc.,) should be dreaded. In children for example, such
an exposure would lead to adverse health consequences against the developing
brain, which may result in long-term cognitive deficits as evidenced in literatures.
|| Pb, Cd and Hg contents in Kaolin samples in various district
|Values in the same column having the same superscripts are
not significantly different (p<0.05)
|| Pb, Cd and Hg contents at conditioning and harvest mines
|Values in the same column having the same superscripts are
not significantly different (p<0.05)
Elevated blood lead is known to damage a childs central nervous system,
kidneys and reproductive system. At higher levels it can even cause coma, seizures
or death (Golub, 2005). Kaolin consumers are therefore
likely to suffer from these manifestations if we consider the high level of
lead found in kaolin on Table 1. Also women of child bearing
age, their fetuses and the elderly are susceptible to lead poisoning, given
that lead is stored in the bone for 10-20 years after initial exposure and high
levels of lead can be released into the blood during bone loss in pregnancy
and in old age. There is a strong relation between maternal and umbilical cord
blood lead levels, indicating the transfer of lead from mother to fetus (Gardella,
2001). Lead levels in the blood are also known to correlate with the lead
level in maternal blood posing an additional risk to the neonate (Li
et al., 2000), this situation is tragic to innocent neonates who
will be susceptible to lead poisoning because of the nutritional habit of their
High concentration of cadmium on its part exerts detrimental effects on human
health and causes severe diseases such as tubular growth, kidney damage, cancer,
diarrhea and incurable vomiting. Cadmium as well can cause damage to all types
of body cells. It damages the cell membrane and increases the permeability of
the cells, the consequence being that the transfer of the other heavy metal
elements into the cells is facilitated. In acute stage, cadmium intoxication
causes enteritis (Bhattachargya, 1983). As oral exposure
risk level for cadmium becomes high, consumers become susceptible to all the
other heavy metal poisoning. Increased concentration of cadmium has been found
in the placenta of women who have given birth to children with low birth weight,
neural damage and Downs syndrome. Children who are exposed to large concentrations
of cadmium in their environment often have learning disabilities (Massanyi
et al., 2007). Women who consume a lot of kaolin especially when
they are pregnant (as revealed in our pilot study by questionnaire) are together
with their children susceptible to cadmium and other heavy metal poisoning.
The concentrations of mercury exceeding the maximum permissible limit (0.03
μg g-1), oral exposure, cause serious health problems such as
loss of vision, hearing and mental retardation and finally death occurs. Mercury
is a toxic substance which has no known function in human biochemistry or physiology
and does not occur naturally in living organisms. Inorganic mercury poisoning
is associated with tremors, gingivitis and/or minor psychological changes, together
with spontaneous abortion and congenital malformation (Vermeire
et al., 1991). Monomethylmercury causes damage to the brain and
the central nervous system, while foetal and postnatal exposure have given rise
to abortion, congenital malformation and development changes in young children
(Baars et al., 2001). Since the risk level for
Hg is very high consumers of kaolin and their subsequent generations will suffer
from these manifestations, except for the fact that its major pathway into the
bodys blood is by inhalation.
This investigation shows that kaolin in is highly consumed by the population and contains high amounts of lead, cadmium and mercury, which are known to be very toxic to humans. It is therefore imperative that further studies be carried out (e.g., blood level of these minerals amongst consumers etc.), so as to determine the exact risk level(s). Since these heavy metals are not easily eliminated by the human system, there is a need for the serum investigation of these heavy metals in those countries where this phenomenon is a habit (Public Health problem that can be controlled with chelating drugs). Because of high amount of lead, cadmium and mercury, there is need for further investigation on other chemical contaminants; arsenic content, copper content iron content etc.
AOAC, 1984. Official Methods of Analysis of the Association of Official Agricultural Chemists. 12 Edn., AOAC, Washington, DC.
ATSDR/DTEM, 2006. ToxFAQs: Chemical Agent Briefing Sheets (CABS) - Lead - Redirect. Agency for Toxic Substances and Disease Registry/Division of Toxicology and Environmental Medicine. http://www.atsdr.cdc.gov/cabs/lead/.
Angle, C.R., M.S. Mclntire and A.V. Colucci, 1974. Lead in air, dust fall, soil, house dust, milk and water: Correlation of blood lead in urban and suburban school children. Trace Substan. Environ. Health, 8: 23-29.
Azumi, S.D. and M.H. Bichi, 2010. Industrial pollution and heavy metals profile of challawa river in Kano, Nigeria. J. Applied Sci. Environ. Sanitation, 5: 23-29.
Direct Link |
Baars, A.J., R.M.C. Theelen, P.J.C.M. Janssen, J.M. Hesse and M.E. van Apeldoorn et al., 2001. Re-evaluation of human-toxicological maximum permissible risk levels. RIVM Rapport 711701025, March 2001. https://www.rivm.nl/bibliotheek/rapporten/711701025.pdf.
Banenzoue, 1992. Reactivity in acid diluted edible clays in Cameroon: Determination of iron and zinc absorbed. Masters Thesis, University of Yaounde, Cameroon.
Bhattachargya, M.H., 1983. Metabolism and toxicity of cadmium and lead during pregnancy and lactation. Fed. Proc., 42: 1726-1729.
Bornschein, R., 1986. Lead in soil in relation to blood lead levels in children. Trace Substan. Environ. Health, 20: 322-332.
Burtis, C.A. and E.R. Ashwood, 2001. Tietz Fundamentals of Clinical Chemistry. 5th Edn., Palme Yayincilik, Ankara, Turkey, ISBN: 9780721686349, Pages: 1091.
Chaney, R.L., H.W. Mielke and S.B. Sterrett, 1989. Speciation, mobility and bioavailability of soil lead. Proceedings of the International Conference on Lead in Soils: Issues and Guidelines, March 7-9, 1988, Environment Geochemical Health, Chapel Hill, NC -.
DME, 2005. South Africa's mineral industry 2004/2005. Department of Minerals and Energy, Republic of South Africa, pp: 148-154, http://www.infomine.com/publications/docs/DMESouthAfrica/DME_Annual_Report_0405.pdf.
Danford, D.E. and A.M. Huber, 1982. Pica among mentally retarded adults. Am. J. Ment. Defic., 87: 141-146.
Davies, B.E., 1990. Lead. In: Heavy Metals in Soils, Alloway, B.J. (Ed.). Blackie and Son Ltd., Glasgow/London, pp: 177-196.
EDF, 1990. Legacy of lead: America's continuing epidemic of childhood poisoning. Environmental Defense Fund, Washington DC.
EPA, 2006. Analysis plan for human health and ecological risk assessment for the review of the lead national ambient air quality standards. U.S. EPA Office of Air Quality Planning and Standards Research Triangle Park, NC., http://www.epa.gov/ttnnaaqs/standards/pb/data/pb_analysis_plan_053106.pdf.
Eleni, I., M. Aletrari and C. Eftychia, 2006. Risk assessment of the dietary intake of lead, cadmium, mercury and nitrates in cyprus and the relevant uncertainty. Proceedings of the AOAC Europ Section, Internationa Workshop, November 6-7, 2006, Limassol -.
FAO/WHO, 1993. Evaluation of certain food additives and contaminants. Proceedings of the 41st meeting of the Joint FAO/WHO expert committee on food additive. WHO Technical Report Series 837, pp: 28-30.
FAO/WHO., 1999. Expert committee on food additives, summary and conclusions. Proceedings of the 53rd Joint FAO/WHO Expert Committee on Food Additives Meeting, June 1-10, 1999, Rome, Italy -.
Gamiz, E., E. Caballero, M.D. Rodriguez and C.F.R. Delgado, 1988. Characterization of Spanish kaolins for pharmaceutical use. I. Chemical and mineralogical composition, physico-chemical properties. Bollettino Chimico Farmaceutico, 127: 114-121.
Gardella, C., 2001. Lead exposure in pregnancy: A review of the literature and argument for routine prenatal screening. Obstet. Gynecol. Surv., 56: 231-238.
Golub, M.S., 2005. Metals, Fertility and Reproductive Toxicity. Taylor and Francis, Boca Raton, ISBN: 9780415700405, pp: 153.
Holmgren, G.G.S., M.W. Meyer, R.L. Chaney and R.B. Daniels, 1993. Cadmium, lead, zinc, copperand nickel in agricultural soils of the United States of America. J. Environ. Qual., 22: 335-348.
Direct Link |
Hooda, P.S., C.J.K. Henry, T.A. Seyoum, L.D.M. Armstrong and M.B. Fowler, 2002. The potential Impact of Geophagia on the bioavailability of iron, zinc and calcium in human nutrition. Environ. Geochem. Health, 24: 305-319.
Johnson, D.E., J.B. Tillery and R.J. Prevost, 1975. Levels of platinum, palladium and lead in populations of Southern California. Environ. Health Presspect, 12: 27-33.
Li, P.J., Y.Z. Sheng, Q.Y. Wang, Y.L. Guly and Y.L. Wang, 2000. Transfer of lead via placenta and breast milk in human. Biomed. Environ. Sci., 13: 85 -89.
Madhaven, S., K. Rosenman and T. Shehata, 1989. Lead in soil: Recommended maximum permissible levels. Environ. Res., 49: 136-142.
Madukosiri, C.H. and T.N. Dressman, 2010. Some biochemical parameters in Gallus domesticus and heavy metal content of oil-polluted areas of Yenagoa, Bayelsa state, Nigeria. J. Life Phys. Sci. Acta SATECH, 3: 124-128.
Direct Link |
Massanyi, P., N. Lukac, V. Uhrin, R. Toman and J. Pivko et al., 2007. Female reproductive toxicology of cadmium. Acta Biol. Hung., 58: 287-299.
Mielke, H.W., J.L. Adams, P.L. Reagan and P.W. Mielke, 1989. Soil-Dust Lead and Childhood Lead Exposure as a Function of City Size and Community Traffic Flow: The Case for Lead Abatement in Minnesota. In: Lead in Soil, Davies, B.E. and B.G. Wixson (Eds.). Environmental Geochemistry and Health, USA, pp: 253-271.
Nweke, F. N., A.N.C. Okaka and E.C. Offor, 2008. Lead, zinc and pH concentrations of enyigba soils in abakaliki local government area of Ebonyi State, Nigeria. Afr. J. Biotech., 7: 2441-2443.
Direct Link |
Usman, O., A. Shuaib and O. Dosumu, 2007. Analysis of lead in soil and selected food samples at Kyaure Mechanic Village, Bauchi state, Nigeria. Nig. J. Pure. Appl. sci., 22: 2059-2062.
Direct Link |
Vermeer, D.E. and R.E. Ferrell Jr., 1985. Nigerian geophagical clay: A traditional antidiarrheal pharmaceutical. Science, 227: 634-636.
Vermeire, T.G., M.E.V. Apeldoom, J.C. Fouw and P.J.C.M. Janssen, 1991. Proposal for the human-toxicological substantiation of C. values toetsings national institute of public health and environmen. R.I.V.M. Report No. 7252010,005, The Netherlands.
Virginia, M., O. Ayhan, T. Yavuz, A. Ayten, C. Suhru, Y. Orhan, R. Fevri and D. Bahtiyar, 1968. Effect of clay upon iron absorption. Am. J. Clin. Nutr., 21: 78-86.
Walker, A.R.P., B.F. Walker, F.I. Sookaria and R.J. Canaan, 1997. Pica. J. Roy Health, 117: 280-284.