Evidence is presented for the photochemical formation of singlet molecular oxygen (1O2) in air-saturated aqueous solutions of several sunscreen active ingredients using sunlight-range illumination. This is of significance because (1) 1O2 is known to be cytotoxic, and (2) there have been several reports of toxic effects associated with the use of some sunscreens; most notably, with p-aminobenzoic acid (PABA). Illuminated aqueous solutions of PABA, 2-ethylhexyl p-(dimethylamino)benzate (ODPABA), 2-hydroxy-4-methoxybenzophenone (BZ3), 2,2'-dihydroxy-4-methoxybenzophenone (BZ8), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (OCR), 2-ethylhexyl p-methoxycinnamate (OMC), and 2-ethylhexyl salicylate (OCS) were evaluated individually for 1O2 formation. Furfuryl alcohol (FFA), a well-known chemical trap for 1O2, was added to each of the aqueous sunscreen solutions. The FFA was consumed when solutions of PABA, ODPABA, OMC, and OCR were illuminated, but no loss of FFA other than by direct photolysis occurred in solutions of BZ3, BZ8, or OCS. There was also no significant loss of FFA in any of these solutions kept in the dark. Further evidence for the formation of 1O2 in illuminated aqueous sunscreen solutions is provided by the results of experiments in which individual solutions containing sunscreen active ingredients and FFA that were diluted with D2O exhibited an increased rate of FFA consumption while the addition of azide ion (N3-) reduced the rate of FFA consumption. Continuous sunlight-range illumination of aqueous PABA solutions produced significantly higher steady-state concentrations of 1O2 than in solutions containing any of the other sunscreen active ingredients evaluated. The substituted benzophenone compounds (BZ3 and BZ8) and the salicylate-based compound (OCS) not only appear to produce no 1O2, but they also appear to produce no other reactive oxidant species that are capable of consuming FFA. This indicates that BZ3, BZ8, and OCS may be peferable, from the standpoint of toxic oxidant formation, for use as sunscreen active ingredients when compared to the other compounds evaluated in this study.

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Formation rates and steady-state concentrations of hydroxyl radical ( • OH) in illuminated surface water samples collected in west-central Indiana that receive acidic mine drainage runoff are reported. Formation rates for • OH in samples were measured by the addition of 1 ϫ 10 Ϫ3 M benzene prior to illumination in order to effectively scavenge all of the • OH formed, thereby yielding phenol. The • OH formation rates were calculated from the measured phenol formation rates. Steady-state concentrations of • OH were measured by the addition of 5 ϫ 10 Ϫ7 M nitrobenzene to the samples prior to illumination. Estimated sunlight • OH formation rates range from 16 M h Ϫ1 to 265 M h Ϫ1 . Estimated sunlight steady-state • OH concentrations range from 6.7 ϫ 10 Ϫ15 to 4.0 ϫ 10 Ϫ12 M. Both the formation rates and steady-state concentrations for • OH are thus two to three orders of magnitude higher than values reported in the literature for other sunlit surface water samples. Due to the very high rates of formation and steady-state concentrations for • OH in these samples, we conclude that aqueous-phase reactions involving • OH represent a significant pathway by which organic pollutants in illuminated surface waters receiving acidic mine drainage runoff may be consumed.

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