FREE RADICALS AND NATURAL SUBSTANCES IN PELOIDS 81 Table X Selected GC-MS of Organic Components in DM and WM Samplesa Compounds m/z (%) Alkanols Decan-1-ol (C10) 140 (7) [M-H2O], 112 (26), 83 (64), 70 (87), 55 (100)b Undecan-1-ol (C11) 154 (8) [M-H2O], 126 (22), 111 (29), 83 (71), 69 (91), 55 (100) Dodecan-1-ol (C12) 168 (13) [M-H2O], 140 (25), 111 (31), 97 (50), 83 (82), 69 (91), 55 (100) 2-Butyl-octan-1-ol (C12) 140 (10) [M-46], 125 (16), 111 (20), 85 (31), 69 (50), 57 (100) Tridecan-1-ol (C13) 182 (12) [M-H2O], 139 (10), 111 (30), 83 (70), 69 (80), 55 (100) Tetradecan-1-ol (C14) 214 (10) [M-H2O], 140 (12), 111 (35), 83 (71), 69 (75), 55 (100) Octadecan-1-ol (C18) 252 (21) [M-H2O], 224 (19), 209 (5), 125 (29), 111 (38), 83 (100) Icosan-1-ol (C20) 298 (2) [M], 280 (24) [M-H2O], 252 (15), 238 (7), 224 (9), 210 (9), 43 (100) Aromatic hydrocarbons Ethylbenzene 106 (32) [M], 91 (100) [M-CH3], 77 (11), 65 (13), 51 (12) m-Xylene 106 (71) [M], 91 (100) [M-CH3], 77 (18), 65 (11), 51 (19), 39 (24) p-Xylene 106 (75) [M], 91 (100) [M-CH3], 77 (13), 65 (7), 51 (10), 39 (10) 1,4-Diethyl benzene 134 (55) [M], 119 (100) [M-CH3], 105 (83), 91 (25), 77 (12) 1,2,4-Trimethyl benzene 220 (35) [M], 105 (100) [M-CH3], 91 (14), 77 (16), 65 (10) Carboxylic acids and ester derivatives Butyl acetate (C6) 73(24), 61 (25), 56 (43), 43 (100) Myristic acid (C14) 228 (42) [M], 185 (20), 129 (51), 73 (100) Palmitic acid (C16) 256 (22) [M], 213 (14), 129 (31), 73 (87), 60 (81), 43 (100) Stearic acid (C18) 284 (31) [M], 255 (11), 241 (14), 185 (18), 129 (32), 43 (100) Ricinoleic acid (C18) 280 (21) [M], 264 (2), 184 (24), 166 (37), 98 (68), 55 (100) Methyl palmitate (C17) 270 (22) [M], 238 (7) [M-CH3OH], 227(19), 87 (74), 74 (100) Methyl oleate (C19) 296 (5) [M], 264 (15) [M-CH3OH], 222 (16), 180 (20), 83 (71), 69 (80), 55 (100) Methyl stearate (C19) 298 (14) [M], 267 (4) [M-CH3OH], 255 (10), 143 (18), 87 (68), 74 (100) Terpenoids Retinol (vitamin A) 284 (100) [M], 269 (12) [M-CH3], 173 (62), 159 (51), 145 (48), 119 (67) Retinoic acid 300 (100) [M], 285 (27) [M-CH3], 256 (22) [M-CO2], 185 (28), 145 (47) Retinol acetate 328 (16) [M], 268 (100) [M-COOH], 253 (24) [M-COOH-CH3], 197 (29), 145 (67), 119 (63) Methyl retinoate 314 (100) [M], 299 (14) [M-CH3], 255 (23), 177 (20), 159 (18), 119 (26) Gibberellic acid 346 (8) [M], 328 (14) [M-H2O], 300 (15), 284 (13), 152 (28), 136 (100), 121 (61) Limonene 136 (21) [M], 121 (22) [M-CH3], 107 (21) [M-2xCH3], 93 (45), 68 (100) β-Carotene 536 (100) [M], 444 (23), 430 (8), 378 (9), 268 (13), 105 (64) α-Tocopherol 430 (35) [M], 205 (8), 165 (100), 149 (5), 136 (7), 121 (9) Phenols Salicylic acid 138 (90) [M], 120 (100) [M-H2O], 92 (83), 64 (27), 39 (23) Gallic acid 170 (45) [M], 152 (100) [M-H2O], 124 (37), 106 (28), 95 (13), 48 (31) Gallaldehyde 154 (100) [M], 136 (9) [M- H2O], 125 (14), 108 (13), 79 (18), 51 (12) Phenol 94 (100) [M], 66 (44), 55 (8), 39 (33)

JOURNAL OF COSMETIC SCIENCE 82 Compounds m/z (%) Hydroquinone 110 (100) [M], 81 (37), 55 (26), 39 (24), 27 (21) 2,4-Dimethylphenol 122 (90) [M], 107 (100) [M-CH3], 103 (8), 91 (23), 77 (38) Thymol 150 (29) [M], 135 (100) [M-CH3], 115 (9), 91 (18), 77 (8) Alkaloids Colchicine 399 (54) [M], 371 (46) [M-H2O], 340 (8) [M-CH3CONH2], 312 (100), 297 (51), 281 (46), 269 (28) a Mass spectroscopy was performed by using a Varian apparatus. The abundance of peak is reported in parenthesis. b Analytical tools in experimental. Table X Continued Alkanes and alkenes have no signifi cant antioxidant properties. However, some long car- bon chain derivatives (C8–C10) are applied in cosmetics (or drugs) to make the formula- tions homogeneous (47), and are components of vegetable extracts, such as propolis (48). The absence of specifi c petroleum biomarkers, hopanes, homohopanes, steranes, and ter- panes (49), suggests that the main sources of long chain alkanes in DM are plant wax compounds (50). The polar and nonpolar fractions of the WM peloid were identifi ed as previously reported for the DM sample (Tables XI and XII). The extraction yields are reported in the Materials and Methods. The m/z values and peak abundances are provided in Table X. In the polar fractions, we identifi ed alkanes, alkanols, aromatic hydrocarbons, phenols, alkaloids, terpenoids, acids (and ester derivatives), and two sulfur derivatives (hexathione and octathione). The highest amount of compounds was detected in acetone (1.63 mg), followed by MeOH (0.72 mg) and EtOAc (0.19 mg) (Table XI). Terpenoids were the main component (for a total amount of 0.45 mg). Among the acid derivatives, the presence of 2-amino-4-mercaptobutyric acid (homocysteine) suggests the incorporation of sulfur (i.e., an abundant component in natural peloids) in a secondary metabolite. Homocysteine stimulates the antioxidant element–mediated expression in macrophages (51), and inhibits Cu2+-dependent oxida- tion of human low-density lipoproteins (52). Tocopherols (vitamin E) are characterized by high antioxidant activity (53) and are used in prevention and therapy of aging (54), in- fl ammatory (55) and cancer (56) diseases. Similarly, β-carotene shows high antioxidant activity and radical scavenging properties in UV solar radiation–mediated damage (57), as well as in the prevention of melanoma (58). The antioxidant and anticancer properties of limonene (one of the main component of essential oils) are widely reported (59). About the composition of the nonpolar fractions, we identifi ed alkanes and alkenes, besides to minor amounts of alkanols and carboxylic acids and esters derivatives. The highest amount of compounds was in diisopropyl ether (0.94 mg), followed by cyclohexane (0.58 mg) and heptane (0.10 mg). It is interesting to note that, irrespective to the nature of the sample, DM and WM peloids showed an amount of bioactive compounds several order of magnitude higher than that previously reported for mud samples produced by artifi cial procedures (i.e., synthetic clay maturated in thermal water for several months) (8). Moreover, most of the natural substances with antioxidant activity (terpenoids, phenols, and fatty acids) were concentrated in the polar fractions.