Relationship of Lead and Cadmium to Essential Elements in Hair, Teeth, and Nails of Environmentally Exposed People

Ecotoxicology and Environmental Safety 46, 265}274 (2000) Environmental Research, Section B doi:10.1006/eesa.2000.1921, available online at http://www.idealibrary.com on

Relationship of Lead and Cadmium to Essential Elements in Hair, Teeth, and Nails of Environmentally Exposed People Barbara Nowak and Jadwiga Chmielnicka* Department of Toxicology, Silesian University of Medicine, 41-200 Sosnowiec, JagiellonH ska 4, Poland; and *University of Medical Academy, 90-145 %o& dzH , MuszynH skiego 1, Poland Received July 15, 1999

The aim of this investigation was to evaluate the environmental exposure to Pb and Cd during 1990+1997 of inhabitants of Katowice District, which is an area of high environmental exposure to lead and cadmium, as well as exposure to Fe, Zn, Cu, Mn, Ni, Cr, Ca, Na, and K, on the basis of concentrations in hair, teeth, and nails. This investigation was to explain if accumulation of Pb and Cd can a4ect the concentration of such essential metals as Fe, Zn, Cu, and Ca. Inhabitants of the Beskid area constituted a control group. Analysis of the aforementioned elements was carried out on 624 hair samples, 785-toothsamples, and 338 nail samples taking into consideration sex, age ( < 15, 16+30, > 30 years), and type of teeth (incisor, canine, molar, premolar). Concentrations of elements in the media investigated were determined using atomic absorption spectroscopy. The results were calculated using the Statistica program. The major statistical analysis focuses on determining analysis of variance by MANOVA/ANOVA, Rao R ( P < 0.05), Spjotvolla+Stoline:a test, and cluster analysis (1-Pearson r). The investigation revealed that among the media investigated, Pb concentration in hair is an environmental marker of exposure to this metal in the human organism and depends on sex and age. It was also observed that an increase in Pb concentration in hair causes a decrease in Fe and Ca concentrations and changes the ratios of essential metals: Fe/Cu, Fe/Zn, and Ca/Zn. It is concluded that not only in blood but also in the hair, lead signi5cantly in6uences Ca and Fe. Analysis of nail samples of people living in Katowice District indicated that an increasing concentration of Pb decreases concentrations of copper and zinc. Increased accumulation of such metals as Ni, Cr, and Mn in teeth was observed for samples taken from inhabitants of Katowice District.  2000 Academic Press Key Words: heavy metals; human hair; human teeth; human nails; ratios of toxic to essential metals; ratios of essential to essential metals; MANOVA; cluster analysis. INTRODUCTION

The impact of environmental exposure to toxic metals on human health has been discussed in numerous publications  To whom correspondence and reprint requests should be addressed.

over the past 20 years, especially with respect to lead (IPCS, 1995) and cadmium (Ha"atek and Chmielnicka, 1993; IPCS, 1992; Buchet et al., 1983; Nishijo et al., 1999). Evaluation of the toxic e!ects of Pb and Cd on people living in polluted areas is based mainly on analysis of the concentrations of those metals in blood and urine and the accompanying biological e!ects (Minoia et al., 1990; Hamilton et al., 1994). Hair, teeth, and nails can accumulate not only toxic metals such as Pb and Cd but also essential metals such as Zn, Cr, Fe, Ni, Co, Cu, Mn, Ca, Na, and K and can be taken into consideration when evaluating environmental pollution. Data on the concentrations of metals in hair, teeth, and nails are found in the following papers from various countries: Hair: ;nited States (Iyengar et al., 1991, 1978; Katz and Katz, 1992; Paschal et al., 1989; Vance et al., 1988; Tuthill, 1996). Italy (Perrone et al., 1996; Caroli et al., 1992, 1994; Piccini et al., 1996; Contiero and Folin, 1994). Germany (Wilhelm et al., 1994; Palusen et al., 1996; Krause et al., 1992). Spain (Schuhmacher et al., 1996). Austria (Wolfsperger et al., 1994). India (Sukumar and Subramanin, 1992). Iran (Raie, 1996). Hong Kong (Man et al., 1996). China (Zhuang et al., 1990). Czech Republic (Kuc\ era et al., 1988). Poland (Kozielec et al., 1996, 1994; Graczyk et al., 1993; Radomska et al., 1991; Zachwieja et al., 1995). ¹eeth: ;nited States (Bellinger et al., 1994; Rabinowitz et al., 1993). >ugoslavia (Balanus\ a, 1990). Spain (Gil, 1996). Israel (Berkovitz and Laufer, 1993). Australia (Gulson and Wilson, 1994). Germany (Ewers et al. 1990). Great Britain (Lane and Peach, 1997). Poland (GlenH -Haduch et al., 1997; Owczarczak, 1988; Struz ak WysokinH ska and Kot, 1987). Nails: ;nited States (Vance et al., 1988; Garland et al., 1993; Iyengar et al., 1978; Chaudhary et al., 1995). Germany (Wilhelm et al., 1994). India (Sukumar and Subramanin, 1992). Nigeria (Oluwole et al., 1994). Japan (Hayashi et al., 1993). Denmark (Garmmelgard et al., 1991). Poland (D!bkowska et al., 1993). This literature indicates that there are no data demonstrating that Pb and Cd exposure can result in changes in the concentrations of metals such as Zn, Fe, Cu, and Ca,

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which are essential to the human body. Generally, there are no data that take into consideration the relationship of those toxic metals to essential metals in easily available biological media such as hair, nails, and teeth. People are exposed to toxic metals in the environment via food, air, water, and soil. The Katowice District is Poland's most polluted region; Cd and Pb concentrations in soil and air are very high according to Gzyl (1997) and the Report of WSEE in Katowice (1997). The new data acquired for a large population of children (n'7000) in Katowice District reveal concentrations of Pb in blood of 62.20}67.10 lg/L (Zejda et al., 1997). Blood Pb concentrations for an adult population in the town of Szopienice (Katowice District) averaged 101.70 lg/L and were greater in comparison with other districts in Poland (Jakubowski, 1993). Increased susceptibility to caries in teeth of children living in districts where exposure to lead is high (Katowice District) has been reported (BaranH skaGachowska et al., 1987). Inhabitants of Katowice District are at higher risk of contracting neoplastic and respiratory system diseases according to Zem"a (1995). Infant morality is higher than average and the life span in Katowice District is shorter than the average for Poland (Norska-BoroH wka, 1994; Bursa, 1994). The aim of this paper was to analyze such biological media as human hair, teeth, and nails and to con"rm whether these media could be used as indexes of environmental exposure to lead and cadmium. Concentrations of the toxic metals Pb and Cd and some essential metals such as Zn, Cu, Fe, Mn, Ni, Co, Cr, Ca, Na, and K were analyzed

in easily available biological media taken from people living in areas with di!erent levels of environmental pollution. The environmentally exposed population (Katowice and Sosnowiec) was examined. Inhabitants of the Beskid area (Bielsko District) were not as environmentally exposed to the aforementioned metals as inhabitants of Katowice District and they make up the control group. MATERIALS AND METHODS

Characteristics of the investigated groups are listed in Table 1 (n"624, hair; n"785, teeth; and n"338, nails). Only healthy people for whom health records were available were included, and only those samples from people born and living in the investigated area were selected. Procedures for collecting and analyzing samples are reported elsewhere: hair (Nowak, 1996, 1998a; Nowak and Koz"owski, 1998), teeth (Nowak, 1995, 1996; Nowak and Koz"owski, 1998); nails (Nowak, 1996). Concentrations of metals in these media are expressed as micrograms per gram of dry matter. Hair Hair samples were obtained from people who did not have colored or treated hair. The age and sex of each donor were recorded. Samples were collected from the nape of the neck and washed using acetone and distilled water. Hair was digested in a Te#on vessel with nitric acid, and perchloric acid was added to the resultant solution. For determination of Ca in every medium investigated, lanthanum

TABLE 1 Characteristics of Human Groups Investigated a Hair Region

Total

Teeth

Age@

SexA

Total

Age

Nails

Sex

Type of teethB

Total

Age

Sex

Katowice and 184 Sosnowiec

(1) (2) (3)

41 59 83

M K

86 97

334

(1) (2) (3)

51 82 198

M K

162 169

T P S K

136 58 76 61

112

(1) (2) (3)

21 57 34

M K

46 66

Beskid

440

(1) (2) (3)

74 148 217

M K

202 188

451

(1) (2) (3)

78 105 271

M K

189 204

T P S K

225 51 71 107

226

(1) (2) (3)

55 85 86

M K

105 121

Total

624

(1) (2) (3)

115 207 301

M K

262 286

785

(1) (2) (3)

129 187 469

M K

351 373

T P S K

361 109 147 168

338

(1) (2) (3)

76 141 111

M K

161 177

? All values are numbers of samples. @ (1) up to 15 years, (2) 16}30, (3) above 30 years. A K, female; M, male. B T, molar; P, premolar; S, incisor; K, canine.

267

RELATIONSHIP OF Pb AND Cd TO ESSENTIAL ELEMENTS

TABLE 2 Detection Limit and Absorption Lines Used for AAS Analysis (Philips Pye Unicam SP 9-800)

Metal Pb Cd K? Na? Ca? Co Cr@ Cu Fe@ Mn Zn Ni

Lamp current (mA)

Spectral bandpass (nm)

Absorption line (nm)

4 8

0.5 0.5

217.0 228.8

9 10 16 16 10 10 16

Detection limit (lg/g)

0.2 0.5 0.5 0.5 0.5 0.5 0.2

Hair 2.0 0.24 40 7.0 80.0 0.04 0.04 0.46 1.6 0.40 0.40 0.40

240.7 357.9 324.7 248.3 279.5 213.9 232.0

Nails 1.4 0.16 50 4.0 36.0 0.02 0.02 0.28 0.88 0.46 0.22 0.21

Teeth 3.0 0.38 40 9.4 100.0 0.06 0.06 0.44 1.86 1.0 0.36 0.44

? Emission measurement, time constant 0.2 s. @ Without background corrected.

was digested with HNO . The solution obtained was di luted with distilled water to 10 ml. Concentrations of metals were analyzed by atomic absorption spectroscopy (AAS) (Philips Pye Unicam SP-9). Table 2 lists the detection limits and absorption lines used for AAS analysis. Statistical Analysis Results were analyzed using the Statistica version 5.0 program. Stanisz (1998). The essential di!erence in accumulation of metals and some ratios of micro- to macroelements in the human media investigated (hair, teeth, nails), for populations living in di!erently polluted areas, were calculated using ANOVA/MANOVA, Rao-R, and the Spjotvolla-Stoline'a (P(0.05). Cluster analysis (1-Pearson r, r-coe$cient of correlation) is a technical description of correlations between groups. RESULTS

chloride was added to make a "nal sample concentration of 1%. Teeth Teeth were extracted at dental o$ces. Age, sex, type of teeth (incisor, canine, molar, premolar), and place of residence were determined for each donor. Powdered teeth were dried at 853C to a constant mass and digested with nitric acid. Nails Nail samples were collected from all 10 "ngers. They were washed in 1% Triton X-100 and acetone. Dried material

Control Group (Inhabitants of Beskid) Average donor age in the control and exposed groups ranged from 25 to 36.8 years depending on the medium. In the control group (inhabitants of Beskid) accumulation of such elements as Pb in the media examined was in#uenced by age, sex, and, in the case of teeth, also by type of teeth. The concentrations of metals in hair of Beskid inhabitants were (Pb) 4.8 lg/g and (Cd) 0.55 lg/g (Table 3). In subjects older than 30 years, higher concentrations of Pb were observed in hair in comparison with younger individuals. In the control group higher concentrations of toxic metals were observed in hair of males (Pb, 5.20 lg/g; Cd, 0.65 lg/g) in comparison with females (Pb, 4.3 lg/g; Cd, 0.45 lg/g). However, essential metals, such as Fe, Mn, Cr, and Ca, were

TABLE 3 Average (ⴞSD) Concentrations of Metals in Hair, Teeth, and Nails for People Living in Di4erently Polluted Regions in Poland Hair (lg/g) Metal Pb Cd Fe Cu Co Cr Mn Zn Ni K Na Ca

Teeth (lg/g)

Nails (lg/g)

Beskid

Katowice

Beskid

Katowice

Beskid

Katowice

4.8$3.4 0.55$0.86 51.2$34.3 7.2$6.2 0.7$0.9 1.1$1.6 2.5$2.2 124.8$150.6 1.1$5.4 102.9$114.5 264.4$162.5 793.8$827.2

5.7$2.2 0.56$2.3 22.5$13.3 7.2$2.7 0.03$0.09 0.4$1.34 1.4$0.9 132.7$135.7 0.6$2.4 96.7$45.2 214.9$156.6 567.8$507.7

36.3$11.5 2.5$1.2 29.9$16.9 5.6$13.7 6.3$2.7 22.9$18.8 4.6$3.0 287$507 4.9$1.9 85.5$78.7 1584$1249 144,504$93,621

36.5$16.3 3.1$5.8 40.7$41.6 6.2$14.1 5.9$2.3 49.5$22.5 5.9$4.0 328$325 6.1$3.5 81.0$101.1 18,653$2,194 135,322$113,924

8.7$10.2 2.1$3.7 143.7$109.4 7.0$4.3 0.58$2.2 46.8$50.1 13.6$16.0 117.4$41.4 2.1$4.2 391.4$264.6 1,188$572 930.7$447

11.2$8.1 1.2$1.3 117.8$73.8 4.3$4.3 0.3$1.1 18.1$42.2 13.6$11.6 99.5$52.9 5.0$4.3 431$171 993$300 957.2$514

268

NOWAK AND CHMIELNICKA

present in higher concentrations in females: Fe, 53.67 lg/g; Mn, 3.04 lg/g; Cr, 1.29 lg/g; Ca, 939.3 lg/g. Sex in#uenced the concentrations of metals in nails. In males, lead content was 10.25 lg/g, and cadmium, 2.44 lg/g, and these values were higher in comparison with those for females. Analysis of essential metals in nails revealed signi"cant statistical di!erences (ANOVA, P(0.05). The concentration of zinc in nails in males was 119.2 lg/g, and that in females, 113.3 lg/g. Concentrations of Pb and Cd in teeth in the control group depended on age and type of teeth (MANOVA, Spjotvolla-Stoline'a test, P(0.005). Pb concentrations in incisors, canines, molars, and premolars were respectively 41.8, 37.5, 35.3, and 32.0 lg/g. Cadmium concentrations were 2.5 lg/g in molars, premolars, and canines and 2.8 lg/g in incisors. The highest concentrations of essential metals were those of Zn and Fe in incisors: 483.0 and 31.2 lg/g, respectively. Age clearly in#uenced the concentration of Pb in teeth. The Pb concentration was highest in individuals older than 30 years (36.5 lg/g); the Cd concentration was 2.6 lg/g. Environmentally Exposed Group (Inhabitants of Katowice and Sosnowiec) Figure 1 illustrates the lead concentrations in hair of inhabitants of the polluted area with respect to age (415 years, 16}30 years, '30 years) and sex. Lead concentrations in hair of subjects from the exposed group di!ered signi"cantly from those of the control group (MANOVA, Spjotvolla-Stoline'a test, P(0.005). The mean concentration of lead in inhabitants of Katowice was 5.7 lg/g, about 20% higher than that of inhabitants of Beskid. There were no statistically signi"cant di!erences in Cd concentrations in hair between the groups (ANOVA, P(0.05). There were signi"cant di!erences in hair concentrations of Ca and Fe (MANOVA, Spjotvolla-Stoline'a test, P(0.005). The mean concentrations of these elements were 30}50% lower than those of the control group. In environmentally exposed individuals mean lead and cadmium concentrations were not statistically signi"cant in teeth (Table 3). The concentrations of Mn, Cr, and Ni in teeth of inhabitants of the polluted area were signi"cantly di!erent from the concentrations for inhabitants of the control area (MANOVA, Spjotvolla-Stoline'a test, P( 0.005). In teeth of inhabitants of the polluted area there were respectively 5.9 lg/g manganese, 49.5 lg/g chromium, and 4.9 lg/g nickel, (Table 3). Cluster analysis revealed higher concentrations of Mn and Cr in teeth in the exposed group compared with the control group, and this is con"rmed by the smaller linkage distance of binding in Fig. 2, which is also con"rmed by previous "ndings (Nowak, 1998, 1996). Fingernails of inhabitants in the polluted area contained, signi"cantly higher lead concentrations (11.2 lg/g) than

FIG. 1. Categorized plot for variable Pb in human hair (lg/g).

those of the control group (Table 3). Also, with respect to concentrations of Cd in nails, there were no statistically signi"cant di!erences between exposed individuals and the control group. Lead concentrations depended on the donor's age and place of residence (Fig. 3) (MANOVA, Spjotvolla-Stoline'a test, P(0.005). Concentrations of Cu (4.3 lg/g) and Zn (99.5 lg/g) in nails were lower in the exposed group than in the control group. On the basis of the results of this research it may be stated that the higher lead concentrations in hair of exposed subjects caused decreases in Fe and Ca levels, which in turn led to di!erent Pb/Fe and Pb/Ca values. Figures 4 and 5 illustrate Pb/Fe as well as Pb/Ca ratios in hair of inhabitants of the two areas examined. The mean Pb/Ca ratio in hair of inhabitants of Beskid was 6.03;10\, and that for inhabitants of Katowice was 10.02;10\. Mean Pb/Fe ratios were 9.35;10\ in inhabitants of Beskid and 25.28;10\ in inhabitants of Katowice. Increases in lead concentrations in nails also caused lower Zn and Cu levels (Table 3). In "ngernails, signi"cant di!erences were observed for Pb/Cu and Pb/Zn: in Beskid inhabitants, Pb/Cu"12.4;10\ and Pb/Zn"74.1;10\; In Katowice inhabitants, Pb/Cu"26;10\, Pb/Zn"112.5 ;10\. Ratios of essential metals in hair also changed as a result of toxic metal activity. Fe/Cu (Fig. 6), Fe/Zn (Fig. 7), and

RELATIONSHIP OF Pb AND Cd TO ESSENTIAL ELEMENTS

269

FIG. 2. Cluster analyses for metals in teeth for inhabitants of (a) Katowice and (b) Beskid. Complete linkage, 1!Pearson r.

Ca/Zn (Fig. 8) di!ered signi"cantly between inhabitants of the exposed groups and the control group. Figures 6}8 illustrate the ratios for metals mentioned above for subjects from the exposed group in relation to the control group with respect to age and sex. The mean Fe/Cu ratios are 7.1 in inhabitants of Beskid and 3.2 in inhabitants of Katowice. Fe/Zn"41.0;10\ and 16.9;10\ and Ca/Zn"6.4 and 4.2 for the control group and exposed group, respectively. On the basis of these data it can be concluded that there was less Fe and Ca in the hair of exposed subjects than in the hair of the control group. DISCUSSION

The information presented in the Introduction on the environmental status of Katowice District (Dudkiewicz

et al., 1997; Gzyl, 1997; Report of WSEE Katowice, 1997) was con"rmed by the results of the examinations and demonstrated signi"cant environmental impact on accumulation of the examined toxic and essential elements in hair, teeth, and "ngernails in the polluted areas. The fact that hygienic standards for toxic metals in Katowice District are exceeded was con"rmed by metal accumulation in the media examined, especially hair and "ngernails (Table 3). The data taken from the literature on ranges of toxic and essential metal concentrations in the media examined indicate signi"cant di!erences among the various countries. In case of toxic metals in hair, values quoted by two sources may be 100-fold di!erent. For other elements examined the values are also very di!erent. This is due to a number of parameters*sex, age, "nancial status, dietary habits, and environmental status (food, air, water, soil)*that were

270

NOWAK AND CHMIELNICKA

FIG. 4. Categorized plot for variable Pb/Fe in human hair.

FIG. 3. Plot of mean concentration of Pb in human nails (lg/g). RaoR (64,232)"2.77; P(0.0000.

sometimes not taken into account in the literature. However, it must be emphasized that the ranges of toxic and essential metal concentrations related to hair and teeth in some regions of Poland revealed fewer signi"cant di!erences. It should be noted that the data in Table 3, concerning lead and cadmium concentrations in hair [4.8 (Beskid)} 5.7 (Katowice) lg/g lead and 0.55 (Beskid)}0.56 (Katowice) lg/g Cd], are similar to the data obtained from other Polish researchers (Ch"opicka et al., 1998; Kasznia-Kocot et al., 1996; Lech et al., 1996; Kozielec and DrybanH ska-Kalita, 1994). Mean concentrations of essential metals, especially Fe, Cu, Zn, and Ca, in hair of children and (up to 15 years of age) obtained as a result of this study were comparable to concentrations reported in other studies in Poland (Kozielec et al., 1996; Zachwieja et al., 1995). Moreover, essential metal concentrations reported in the reviews of Iyengar (1991), Iyengar et al. (1978) and Caroli et al. (1994) in adult hair did not di!er from the data in Table 3. In the literature there are no data on the relationship between essential and toxic metals in adult hair. Of the analyzed, easily available biological media from individuals living in Katowice District (hair, teeth, nails), it

is hair that may be considered an appropriate medium for lead exposure assessment (Table 3). It was found that mean lead concentrations in the hair of subjects living in the polluted area (Katowice District) are about 20% higher in comparison with the control group. It was observed that as lead concentration in hair increases, Fe and Ca concentrations decrease (Figs. 4, 5). The di!erences in Pb/Fe and Pb/Ca ratios in human hair should depend on the region of residence, age, and sex, as illustrated in Figs. 4 and 5. For the inhabitants of Beskid, the mean Pb/Fe in hair is 9.35;10\, and for Katowice inhabitants, 25.28;10\. The mean Pb/Ca in hair of inhabitants of Beskid was 6.03;10\, and in hair of Katowice inhabitants, 10.02;10\. Data in the literature indicate a relationship between levels of lead in hair and blood, both in the population exposed occupationally Hodkins et al. (1991) and in subjects exposed environmentally (Cabeza, 1991; Bergoni and Borelli, 1989). These authors point to high correlation coef"cients for lead concentrations in blood and hair: in children, r"0.85 for P(0.1, and in adults r"0.72 for P(0.1, respectively. For lead concentration in hair in the exposed population (inhabitants of Katowice and Sosnowiec) as well as on the basis of data in the literature in Europe for concentrations in blood and hair (simultaneously collected samples in some

RELATIONSHIP OF Pb AND Cd TO ESSENTIAL ELEMENTS

271

FIG. 5. Categorized plot for variable Pb/Ca in human hair.

FIG. 7. Categorized plot for variable Fe/Zn in human hair.

regions) (Kasznia-Kocot et al., 1996; Zejda et al., 1997; Ch"opicka et al., 1998; Spe\ va\ c\ kovaH et al., 1997; Teresa et al., 1997; Schuhmacher et al., 1996; Krause et al., 1992;

Jakubowski et al., 1991; Iyengar, 1991; Katz and Katz, 1992; Caroli et al., 1994), there a Spearman-R analysis was carried out. A high coe$cient was obtained as a result of this analysis: R"0.53 for P"0.09 (n"11), for mean lead concentrations of 94.9 lg/L in blood and 8.2 lg/L in hair. A similar dependence for Pb in blood and hair was found for a population in Germany, (Palusen et al., 1996), but not for Cd. The examinations presented in Table 3 do not indicate di!erent cadmium concentrations in the biological media examined between the exposed and control groups. It is interesting to compare the Pb/Fe values obtained in hair in this study with the values obtained in blood and hair by Abdulla and Chmielnicka (1990) [developed on the basis of Iyengar et al. (1978) and Subramanian (1995)]. The following values were obtained: in hair Pb/Fe"9.35;10\ for the control group and 25.28;10\ for the exposed group, respectively. The quantitative ratio Pb/Fe, according to the data of Abdulla and Chmielnicka (1990) (at a mean lead concentration in blood of 100 lg/L), was 23.2;10\ in blood and 17.7;10\ in hair. In this study it was observed that as Pb increases not only Fe but Ca as well decreases. The data in Table 3 make it possible to calculate Pb/Ca values in this medium. Pb/Ca in hair was 6.03;10\ in Beskid and 10.02;10\ in Katowice. According to the data of Caroli (1994) and Iyengar (1978), Pb/Ca ratios in blood ranged from 1;10\} 2;10\ (for a blood Pb concentration of 100}200 lg/L).

FIG. 6. Categorized plot for variable Fe/Cu in human hair.

272

NOWAK AND CHMIELNICKA

sex and age of the individual. Not only in blood, but also in hair, lead signi"cantly in#uences Fe and Ca levels. As lead concentration in hair increases, Fe and Ca concentrations decrease, causing changes in the quantitative ratios between essential metals: Fe/Cu, Fe/Zn, and Ca/Zn. In "ngernails of subjects living in Katowice District, concentrations of copper and zinc decreased as a result of increasing lead concentration. In subjects living in polluted area, accumulation in teeth of such metals as Ni, Cr, and Mn was increased. There was no essential di!erence (P(0.05) in accumulation of Cd in human hair, teeth, and nails for people living in di!erently exposed environments. ACKNOWLEDGMENTS This study was supported by KBN Grants NN 2-002-1999, NN-2-0221999, NN-5-116-1998 to the Silesian Medical School. The authors thank students Ilona Bednarek, Rafa" GoH rny, Zo"a Niemiec, Agnieszka Rams, and Joannna Mitre1 ga, who took part in sampling and preparation of the samples.

REFERENCES

FIG. 8. Categorized plot for variable Ca/Zn in human hair.

As a result the increase in lead content in hair, ratios of essential metals (Fe/Cu, Fe/Zn, Ca/Zn) changed as illustrated in Figs. 6}8. Mean quantitative values of these ratios in hair of the subjects exposed environmentally and the control group are, respectively, inhabitants Fe/Cu"3.2, Fe/Zn"16.9;10\, and Ca/Zn"4.2, and Fe/Cu"7.1, Fe/Zn"41.0;10\, and Ca/Zn"6.4 in Beskid. It was observed that in "ngernails an increase in lead concentration results in lower levels of Zn and Cu. In this study Pb/Zn values in nails were 112.5;10\ (Katowice) and 74.1;10\ (Beskid), and Pb/Cu values were 26.0; 10\ (Katowice) and 12.4;10\ (Beskid). Considering this, a conclusion may be drawn that not only in blood, but also in hair, lead signi"cantly in#uences concentrations of Ca and Fe, which are essential for the proper functioning of the body. This may have signi"cance in the "eld of bioavailability of these elements to the human body. Such essential metals as Fe, Cu, Zn, and Ca have an impact on proper functioning of the hemopoietic system. CONCLUSIONS

Metals polluting the human environment may be accumulated in hair, teeth, and nails. Among the media examined, lead concentration in hair is a marker of environmental exposure to this metal and depends on the

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