Attenuation photochemical potential of Pontal of Paranapanema river waters (Brazil) from agrochemicals: geographical and temporal assessment.

Knowledge of the environmental photochemical fate of pesticides is essential to assess their potential impacts. However, there are few studies in the literature focused on the photochemical attenuation of micropollutants in Brazilian rivers. In this context, this study characterized the surface waters of the Pontal of Paranapanema region (region which concentrates more than 80% of Brazilian sugarcane cultivations), in order to determine its photochemical attenuation potential against micropollutants in different seasons. Thus, the steady-state concentrations of the photochemically produced reactive intermediates (PPRIs) (hydroxyl radical, HO•; singlet oxygen, 1O2, and triplet-excited state chromophoric dissolved organic matter, 3CDOM*), formed in the rivers, were simulated by using the APEX model (Aquatic Photochemistry of Environmentally-occurring Xenobiotics), considering the sunlight irradiance, water chemistry, and depth. Based on our simulations, these concentrations vary between 0.35 × 10-15 and 4.52 × 10-14 mol L-1 for HO•, 1.3 × 10-15 and 1.2 × 10--14 mol L-1 for 3CDOM*, and 2.5 × 10-15 and 2.5 × 10-14 mol L-1 for 1O2. Finally, mathematical simulations were used for predicting persistence of pesticides atrazine (ATZ) and diuron (DIR) in Pontal of Paranapanema surface waters and the half-life times (t1/2) of the pollutants ranged from a few hours to one week.

Sunlight-driven environmental photodegradation of 2-chlorobiphenyl (PCB-1) in surface waters: kinetic study and mathematical simulations.

Polychlorinated biphenyls (PCBs) are a family of highly toxic, resistant, and persistent organic pollutants, among which 2-chlorobiphenyl (PCB-1) is one of the simplest. Most studies on PCBs' photochemistry are limited to their direct photolysis, while the important role of reactive photo-induced species (RPS) (hydroxyl radicals, HO●; singlet oxygen, 1O2; and triplet excited states of chromophoric dissolved organic matter, 3CDOM*) in removing PCBs in natural waters through indirect photolysis has not yet been evaluated. In this work, the rate constants of the reactions between aqueous PCB-1 and RPS were obtained under simulated solar radiation (450-W Xenon lamp and an AM 1.5 global filter) by competition kinetics, and the effects of the initial pollutant concentration and the physicochemical characteristics of the water were investigated. The direct photolysis quantum yield of PCB-1 in the range 290-800 nm was found as 1.60 × 10-2 mol Einstein-1. The value of kPCB-1,HO● = (6.80 ± 0.09) × 109 L mol-1 s-1 is in good agreement with the literature. For 1O2, kPCB-1,1O2 = (1.13 ± 0.20) × 106 L mol-1 s-1, while for 3CDOM*, kPCB-1,3CBBP* = (2.44 ± 0.04) × 109 L mol-1 s-1 and kPCB-1,3AQ2S* = (3.36 ± 0.04) × 109 L mol-1 s-1 were obtained using 4-benzoylbenzoic acid (CBBP) and anthraquinone-2-sulfonate (AQ2S) as CDOM proxies, respectively. These results show that the main pathways involved in PCB-1 photodegradation are the reactions with HO● and 3CDOM* together with direct photolysis. In addition, the photodegradation of PCB-1 in sunlit waters was simulated using the kinetic model APEX (Aqueous Photochemistry of Environmentally Occurring Xenobiotics). According to simulations, a greater influence of the water depth and dissolved organic carbon concentration (DOC) on the persistence of PCB-1 is expected, being only slightly influenced by the concentrations of nitrite, nitrate, and bicarbonate. Finally, based on data reported for Brazilian surface waters, the average half-life (t1/2) of PCB-1 is expected to vary from 2 to 14 days. In particular, the t1/2 in the Paranapanema River is estimated at 7 to 8 days.

Environmental photochemical fate and UVC degradation of sodium levothyroxine in aqueous medium.

The synthetic hormone sodium levothyroxine (LTX) is one of the most prescribed drugs in the world and the most effective in hypothyroidism treatment. The presence of LTX in the environment has become a matter of major concern due to the widespread use of this hormone and by the fact that it is only partially removed in conventional water and sewage treatment plants. However, information regarding the photochemical fate of this hormone in environmental or engineered systems is scarce in the literature. In this work, the sunlight-driven direct and indirect LTX degradation was investigated by determining the photolysis quantum yield, ΦLTX = 3.80 (± 0.02) × 10-5, as well as the second-order kinetic constants of the reactions with hydroxyl radicals, kLTX,•OH = 1.50 (± 0.01) × 1010 L mol-1 s-1 and singlet oxygen, kLTX,1O2 = 1.47 (± 0.66) × 108 L mol-1 s-1. Mathematical simulations indicate that LTX photodegradation is favored in shallow, nitrite-rich, and dissolved organic matter (DOM)-poor environments, with LTX half-life times varying from less than 10 days to about 80 days. LTX removals of 85 and 95% were achieved by UVC photolysis and UVC/H2O2 after 120 min, respectively. Three transformation products, triiodothyronine, diiodothyronine, and diiodotyrosine, were identified during LTX degradation by the UVC-based processes studied. The results herein regarding photo-induced kinetics coupled with environmental fate simulations may help evaluate LTX persistence and also the design of water and wastewater treatment processes.

Direct and indirect photolysis of the antibiotic enoxacin: kinetics of oxidation by reactive photo-induced species and simulations.

The purpose of this study was to investigate the aqueous phase photochemical behavior of enoxacin (ENO), an antibiotic selected as a model pollutant of emerging concern. The second-order reaction rate constants of ENO with hydroxyl radicals (HO●) and singlet oxygen (1O2) were determined at pH 3, 7, and 9. Also, the rate constants of the electron transfer reaction between ENO and triplet states of chromophoric dissolved organic matter (3CDOM*) are reported for the first time, based on anthraquinone-2-sulfonate (AQ2S) as CDOM proxy. The sunlight-driven direct and indirect ENO degradation in the presence of dissolved organic matter (DOM) is also discussed. The results show that direct photolysis, which occurs more rapidly at higher pH, along with the reactions with HO● and 3AQ2S*, is the key pathway involved in ENO degradation. The ENO zwitterions, prevailing at pH 7, show kENO, HO●, kENO,1O2, and kENO,3AQ2S* of (14.0 ± 0.8) × 1010, (3.9 ± 0.2) × 106, and (61.5 ± 0.7) × 108 L mol-1 s-1, respectively, whose differences at pH 3, 7, and 9 are due to ENO pH-dependent speciation and reactivity. These k values, along with the experimental ENO photolysis quantum yield, were used in mathematical simulations for predicting ENO persistence in sunlit natural waters. According to the simulations, dissolved organic matter and water depth are expected to have the highest impacts on ENO half-life, varying from a few hours to days in summertime, depending on the concentrations of relevant waterborne species (organic matter, NO3-, NO2-, HCO3-).