title: Photochemical generation of reactive species upon irradiation of rainwater: negligible photoactivity of dissolved organic matter.
abstract: This paper focuses on the study of the photochemical activity of dissolved organic matter present in rainwater. Formation rates of the reactive species hydroxyl radical (OH(*)), singlet oxygen ((1)O(2)) and dissolved organic matter triplet states ((3)DOM()) were determined by irradiation (UV-A) of wet-only rainwater samples collected in Turin (Italy) in the presence of specific scavengers (benzene, furfuryl alcohol and phenol, respectively). Photo-formation rates of OH(*) ( approximately 3.10(-)(11)Ms(-)(1)) and (1)O(2) ( approximately 10(-)(14)Ms(-)(1)) were lower (1 or 2 orders of magnitude) or largely lower (4 to 10 orders of magnitude) than those determined for fog and cloud samples in previous studies. (3)DOM() formation rate values were either negligible or quite low ( approximately 10(-)(12)Ms(-)(1)) by comparison with those evaluated for surface water samples. Deduced steady-state [OH(*)] were in the same range as those reported for fog samples in the literature (8.7.10(-)(16) to 1.5.10(-)(15)M), while [(1)O(2)] was often several orders of magnitude lower and, therefore, could be considered as negligible. Nitrite (NO(2)(-)) constituted the main source of OH(*) (69 + or - 21 to 138 + or - 36%), and the deduced contribution of DOM was low or nil. All the results obtained in this study tend to demonstrate that DOM (including HUmic LIke Substances, HULIS) present in rainwater is poorly or not photoactive. Therefore, there could be considerable difference between rainwater DOM (HULIS included) and the organic matter present in surface waters, particularly the humic substances, as far as the photochemical activity is concerned.
authors.affiliation: Dipartimento di Chimica Analitica, Università di Torino, Via P. Giuria 5, 10125 Torino, Italy. alexandre.albinet@gmail.com
authors.forename: Alexandre
authors.initials: A
authors.lastname: Albinet
authors.forename: Claudio
authors.initials: C
authors.lastname: Minero
authors.forename: Davide
authors.initials: D
authors.lastname: Vione
mesh_terms: D009930:Organic Chemicals / Q000737:chemistry*; D010777:Photochemistry; D011891:Rain; D012995:Solubility
chemical_list: D009930:Organic Chemicals