Sources and sinks of hydroxyl radicals upon irradiation of natural water samples

Hydroxyl radical formation rates, steady-state concentration, and overall scavenging rate constant were measured by irradiation of surface lake water samples from Piedmont (NW Italy) and nitrate-rich groundwater samples from Moldova (NE Romania). Dissolved organic matter (DOM) was the main source and sink of ˙OH upon lake water irradiation, with [˙OH] being independent of DOM amount. Water oxidation by photoexcited DOM is a likely ˙OH source in the presence of very low levels of nitrate and dissolved iron. Under different circumstances it is not possible to exclude other processes, e.g., DOM-enhanced photo-Fenton reactions. Under the hypotheses of no interaction and absence of mutual screening of radiation, nitrate would prevail over DOM as ˙OH source for a NO3-/DOM ratio higher than 3.3 x 10-5 (mol NO3-) (mg C)-1, DOM prevailing for lower values. Substantial DOM photolability was observed upon irradiation of nitrate-rich groundwater, mainly due to the elevated ˙OH generation rate. For the first time to our knowledge, evidence was also obtained of the photoformation of potentially toxic and/or mutagenic nitroaromatic compounds upon irradiation of natural lake water and groundwater samples, proportionally to the nitrate levels.