Physiological and Behavioral Parameters Affecting the Hair Element Content of Young Italian Population Pasquale Avino 1, Geraldo Capannesi 2, Luigina Renzi 2 and Alberto Rosada 2 1 DIT, INAIL, Rome. E-mail: p.avino@inail.it 2 ENEA, R.C.-Casaccia, Rome
Background Some metals are naturally found in the human body and are essential to the human health. For instance, Iron prevents anemia, whereas Zinc is a cofactor in over 100 enzyme reactions. They normally are at low concentrations (trace metals). In high doses, they may be toxic to the human body or produce deficiencies in other trace metals; for example, high levels of zinc can result in a deficiency of copper, another metal required by the body.
Hair is an ideal tissue for tracing the human health conditions. It can be cut easily and painlessly and the relative clinical results can give an indication of mineral status and toxic metal accumulation following long term or even acute exposure. A Hair Tissue Mineral Analysis (HTMA) is a test measuring the hair mineral content: if a mineral deficiency or excess is present, then it indicates that a mineral deficiency or excess is within the body, or that the minerals are bio-unavailable.
Different authors have found metal and metalloid contents in hair altered by outdoor pollution phenomena such as the levels are significantly affected. The use of hair as biological monitor of the element body concentration at trace and ultra-trace levels, is only possible after opportune washing procedure. The Instrumental Neutron Activation Analysis technique allows to analyze the samples with no chemical-physical pre-treatment, avoiding contamination problems and positive/negative artefacts.
Scope This study would like to deep the relationship between the concentration levels of 32 elements (essential, toxic, environmental) and some physiological parameters (i.e., gender, hair color, hair type and hair treatment) in population nor environmentally neither occupationally exposed.
Hair Sampling & Treatment 131 teenagers (104 males and 27 females) ranging between 15 and 19 years. Before sampling, a questionnaire was submitted to each volunteer. The questionnaire asked some general (i.e., weight, height, age, sex, hair color, hair length) and specific (i.e., residence, residence floor level, diet, drug use, sport activity, hours for indoor and outdoor activity) information; all the donors were no-smokers. This request was necessary for defining the population. Sample preparation: washing in 25 ml acetone for 10 min and rinsing in deionized water. After drying at 40 C for 15 min, each sample is ready for INAA
Check of the methodology in relation to matrix complexity for minimizing the relative matrix effects due to biological variability. The discrepancy between data is below 5% except for As and Hg in the SRM BCR-397 (-6.5% and 5.7%, respectively). Secondary standards: BCR CRM 397 (Human Hair) and IAEA-085. The uncertainty of the methodology has been tested measuring the above secondary standards with solutions of primary standards at different concentrations: all the found data are in agreement with the certified values.
Secondary Standards Element BCR-397 IAEA-085 Our data Certified Δ Our data Certified Δ As 0.29±0.02 0.31±0.02-6.5 0.131±0.006 (0.126) 4.0 Ca 1522±39 1560±40-2.4 903±34 (929) -2.8 Cd 0.534±0.014 0.521±0.024 2.5 n.d. - Co 0.56±0.02 0.55±0.03 1.8 0.155±0.002 (0.156) -0.6 Cr 93±8 91±33 2.2 n.d. - Cu 113±7 110±5 2.7 17.0±1.1 16.8 1.2 Fe 575±4 580±10-0.9 78.7±3.6 79.3-0.8 Hg 13.0±0.8 12.3±0.5 5.7 22.8±1.1 23.2-1.7 Mn 10.9±0.6 11.2±0.3-2.7 9.1±0.7 8.8 3.4 Mo 6.4±0.5 6.6±0.2-3.0 n.d. - Se 2.1±0.1 2.0±0.08 5.0 1.10±0.05 1.07 2.8 Sr 5.04±0.37 5.25±0.07-4.0 n.d. - Ti 13.4±0.9 14.1±0.5-4.9 n.d. - Zn 196±4 199±5-1.5 160±4 163-1.8
Element concentration (µg g -1 ) Published range Male Female Whole Ag 1.06±3.35 0.23±0.42 0.40±1.58 0.005-9.9 Al 7.27±4.18 8.02±6.28 7.86±5.91 - As 0.04±0.08 0.03±0.04 0.04±0.05 0.001-26 Au 0.21±0.30 0.06±0.08 0.09±0.16 0.0005-591 Ba 1.48±2.60 0.33±0.94 0.57±1.50 0.12-29 Br 4.95±4.29 9.63±15.2 8.66±13.8 0.15-490 Ca 2304±1560 812±580 1120±1060 7-10887 Cd 0.09±0.20 0.02±0.06 0.23±0.19 0.01-16.1 Ce 0.10±0.09 0.09±0.11 0.09±0.11 0.007-1.69 Cl 657±503 1862±1146 1600±1150 <3.6-27000 Co 0.15±0.20 0.17±0.26 0.17±0.25 0.002-15 Cr 0.22±0.26 0.15±0.10 0.17±0.15 0.026-65.3 Cu 14.1±12.1 9.56±4.78 10.5±7.11 - Fe 15.3±9.56 16.8±26.4 16.5±23.9 3-2400 Hg 1.47±1.43 0.97±0.62 1.07±0.87 0.03-195 I 0.76±1.01 0.17±0.23 0.29±0.55 0.03->70 K 232±271 335±272 314±274 0.94-2370 La 0.02±0.02 0.03±0.04 0.03±0.03 <0.003-37 Mg 173±201 72±56 93.0±111 1.5-1412 Mn 0.50±0.27 0.40±0.33 0.42±0.32 0.03-81.5 Mo 0.03±0.03 0.05±0.11 0.05±0.10 - Na 329±307 647±545 581±521 0.04-3500 S 48189±1499 48958±1265 48779±1310-0 2 9 Sb 0.07±0.05 0.06±0.06 0.06±0.05 0.007-38 Sc 0.001±0.000 0.001±0.000 0.001±0.000 0.0004-550 Se 1.12±1.63 0.96±1.55 0.99±1.56 0.002-66 Sn 2.45±2.45 2.73±3.13 2.63±2.81 - Sr 3.50±4.96 2.23±3.91 2.49±4.16 0.01-860 Ti 4.12±2.45 9.68±15.2 7.38±11.2 - U 0.02±0.01 0.02±0.03 0.02±0.03 - V 0.09±0.08 0.07±0.07 0.06±0.07 - Zn 232±149 178±46 189±82 <1-1770 The concentration levels determined in this study are in good agreement with previously published ranges in other similar studies. About Mo, V and U rare data are present in literature. These data could be considered the first values in Rome population. On the other hand, scarce data on macrocomponents are present in literature.
Elements such as Sulfur and Zinc show lower standard deviation than the other elements. Variance related mainly to hair structure difference. Three reasons: 1) main constituents of hair matrix; 2) present in all the individuals at concentration levels above 100 µg g -1 ; 3) levels not so much affected by exogenous contributions. For all other elements variances are very high (in many cases the standard deviation is higher than the mean value) meaning the influence of exogenous pollutants to be strong. Concentrations are very low whereas standard deviations large depending on the group characterization Large variance due to gender (male and female), hair color (light brown, dark brown, blonde, black, red), hair type (straight, wavy, curly) and hair treatment (not any, gel, perm, coloring, lightning).
Element concentration (µg g -1 ) Brown Black Blonde Red light (n=27) dark (n=80) (n=13) (n=7) (n=4) Ag 0.29±0.30 0.49±2.00 0.31±0.46 0.25±0.20 0.10±0.03 Al 7.98±5.53 7.61±3.89 9.03±7.62 11.2±16.5 6.28±2.04 As 0.06±0.11 0.03±0.02 0.02±0.02 0.02±0.02 0.04±0.03 Au 0.10±0.12 0.09±0.19 0.06±0.04 0.12±0.15 0.12±0.09 Ba 0.87±1.96 0.37±0.96 1.31±2.97 0.38±0.71 0.00±0.00 Br 5.54±4.92 9.31±16.7 8.53±7.36 11.1±6.0 12.8±17.5 Ca 1776±1776 969±669 1034±882 1074±611 530±210 Cd 0.04±0.11 0.04±0.12 0.01±0.05 0.00±0.00 0.04±0.08 Ce 0.13±0.16 0.09±0.09 0.08±0.09 0.16±0.23 0.06±0.05 Cl 1291±1776 1696±1170 1569±754 2073±1160 2299±1938 Co 0.12±0.17 0.19±0.30 0.09±0.05 0.19±0.20 0.24±0.28 Cr 0.17±0.09 0.16±0.17 0.15±0.04 0.18±0.17 0.26±0.18 Cu 11.6±8.91 10.3±6.7 10.1±5.69 9.95±4.29 13.6±9.61 Fe 17.5±19.3 13.2±5.7 16.2±13.1 18.8±19.9 72.7±121 Hg 1.08±0.61 1.03±0.88 1.44±1.20 1.25±1.09 0.43±0.19 I 0.50±0.76 0.25±0.53 0.26±0.24 0.10±0.11 0.10±0.11 K 258±280 312±242 349±285 458±503 309±333 La 0.03±0.03 0.02±0.02 0.04±0.07 0.06±0.10 0.04±0.03 Mg 145±210 79±52 103±75 79±68 17.6±20.4 Mn 0.41±0.24 0.45±0.54 0.44±0.26 0.45±0.56 0.86±1.13 Mo 0.04±0.04 0.04±0.05 0.06±0.07 0.04±0.05 0.26±0.50 Na 476±426 574±519 609±448 788±633 995±1025 S 53400±8160 52326±7482 43779±16959 48243±10620 43227±16826 Sb 0.07±0.05 0.06±0.06 0.04±0.03 0.05±0.05 0.06±0.02 Sc 0.0011±0.000 8 0.0010±0.000 6 0.0009±0.000 8 0.0016±0.002 1 0.0008±0.000 1 Se 1.17±1.62 0.88±0.66 0.77±0.15 0.78±0.07 0.71±0.04 Sn 0.54±1.77 0.28±1.15 0.00±0.00 0.00±0.00 0.00±0.00 Sr 2.87±5.34 2.28±3.58 2.65±5.51 2.70±2.45 0.76±1.53 Ti 4.21±11.8 1.27±3.48 0.51±1.83 1.38±3.66 0.00±0.00 U 0.02±0.03 0.02±0.02 0.03±0.04 0.02±0.03 0.006±0.008 V 0.09±0.09 0.06±0.07 0.05±0.05 0.07±0.08 0.04±0.05 Zn 240±144 173±46 184±73 188±24 189±14
Some elements, Al, Zn, K and S, show similar values in all the profiles. (light and dark) Brown and black color hairs show very few difference in the element profile as well as the blonde color hair. Red color hairs shows substantially differences among the five different element profiles. In particular, Fe (5-times), Mn (2-times) and Na (2-times) are higher than the other levels in the other hair colors whereas Mg (up to 10-times), Sr (up to 4-times), Ca and Hg (2-times) show lower levels. Hair type does not point out any significant correlation.
Canonical Discriminant Anal Canonical correlation coefficient V1 V2 V3 Ag 0.0396 0.2198-0.0642 Al 0.0305-0.0335-0.0442 As -0.0373 0.1751 0.1585 Au 0.1617 0.4249 0.2573 Ba 0.4618 0.2572 0.0057 Br 0.0046-0.2369-0.0632 Ca 0.6575 0.5013 0.1005 Ce 0.0034 0.0933 0.3697 Cl -0.1472-0.5072-0.0558 Co -0.0217-0.0954 0.1041 Cr 0.0454 0.2723 0.0755 Cu 0.1301 0.2849-0.1042 Fe 0.0023-0.0670-0.0651 Hg -0.0155 0.3351-0.3044 I 0.0734 0.6722 0.0406 K -0.1407-0.1407 0.0493 La -0.0083-0.1701 0.0431 Mg 0.9263 0.1453-0.0196 Mn 0.1025 0.1653 0.0476 Mo -0.0761-0.0413-0.1197 Na -0.0701-0.3035 0.0697 S 0.0512 0.0468 0.0364 Sb 0.0572 0.1384 0.1821 Sc 0.0096-0.0668 0.1186 Se -0.0233-0.0017-0.0418 Sr 0.4621 0.0245 0.2073 U -0.0447-0.0867 0.1395 V 0.1028 0.3226 0.2176 Zn 0.0009 0.4039 0.1757 V1: high correlation coefficients for alkaline-earth metals, i.e., Mg, Ca, Ba and Sr. Good describer of similar behavior of such elements in human metabolism. V2: high correlation coefficients for I, Cl and Ca whereas lower correlation coefficients for Zn, Au, Hg, Ag and V. Good describer of exogenous influences on the population group. V3: any significant correlations.
Principal Component Anal F2 F1
Relationship For determining the influence of pollutants on the human health: correlation between average selected element composition in hair and the content of the same species in some environmental compartments. Table shows both the heavy metals levels in scalp hair and in different environmental compartments, and the linear equations with the relative regression coefficients (R 2 ).
Hair Water Air Food Smoke µg/70-kg standard man As 0.033 2.00 1.60 30.0 21.0 Cd 0.034 3.00 1.80 60.0 3.00 Cr 0.168 15.0 1.10 90.0 1.90 Cu 10.5 200 5.00 3100 15.0 Hg 1.08 0.080 1.00 13.0 0.300 Mn 0.422 110 6.0 3100 130 Sb 0.060 0.320 0.350 34.0 0.450 Se 0.917 0.720 0.130 105 1.00 Sn 0.281 0.080 1.40 1050 Zn 189 500 31.0 14000 10.0 Equation y=2.51x+32.2 y=0.16x+1.8 y=70.6x+727 y=-0.06x+21.7 R 2 0.861 0.966 0.934 0.009
The R2 results are very interesting: Thank you for your kind Ø Poor R related to the correlation among elements and smoke (R = 0.009), confirms no student toattention be smoker. 2 2 Ø Very good correlations with air (R2= 0.966) and food (R2= 0.934) and the good correlation with water (R2= 0.861) demonstrate the direct influence of the environmental local conditions on the levels of essential and toxic elements. These considerations, to be enlarged by comparing all the elements investigated, propose a hypothesis of considering these values as tentative reference values for such elements in hairs of Italian teenagers.