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.

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River, São Paulo, Brazil).

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO●), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23 ± 0.07) × 10-2 and (7.99 ± 1.61) × 10-3 mol Einstein-1, respectively. In contrast, reactions with HO● radicals and 3CDOM* dominate their degradation, with 1O2 exhibiting rates three to five orders of magnitude lower. The values of kIMD,HO● and kAMT,HO● were (3.51 ± 0.06) × 109 and (4.97 ± 0.37) × 109 L mol-1 s-1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with kIMD,3AQ2S* = (1.02 ± 0.08) × 109 L mol-1 s-1 and kIMD,3CBBP* = (3.17 ± 0.14) × 108 L mol-1 s-1; on the contrary, the values found for AMT are close, kAMT,3AQ2S* = (8.13 ± 0.35) × 108 L mol-1 s-1 and kAMT,3CBBP* = (7.75 ± 0.80) × 108 L mol-1 s-1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO3-, NO2-, CO32-, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

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.

Photochemical persistence of sulfa drugs in aqueous medium: kinetic study and mathematical simulations.

This study aimed at investigating the photochemical behavior of sulfa drugs containing five and six-membered heterocyclic substituents (sulfamethoxazole (SMX) and sulfadiazine (SDZ), respectively), in an aqueous medium. Despite their importance, studies devoted to the use of photochemical models to predict the environmental phototransformation of pollutants in surface waters, by combining laboratory results and natural aquatic systems parameters, are still scarce in the scientific literature. In this work, the second-order reaction rate constants of SDZ and SMX with hydroxyl radicals (●OH), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were experimentally determined at pH 7, using the competition kinetics approach. The results show that ●OH and 3CDOM* are the key species involved in sulfonamide degradation, with anionic SMX, most prevalent at pH 6-9, being degraded much slower than the anionic form of SDZ. Moreover, SDZ and SMX photodegradation in natural water samples (spring-fed natural pond, public supply reservoir, and sea water) was significantly enhanced relative to depletion in pure water. Finally, from mathematical simulations of the sunlight-driven sulfonamide degradation, half-life times were predicted for these drugs varying from less than 2 to about 90 days, depending on the water depth, concentration of key species (DOC, HCO3-, NO2-, CO32-) in natural aqueous systems, as well as on the particular heterocyclic substituent.

Removal of sulfadiazine from simulated industrial wastewater by a membrane bioreactor and ozonation.

Ozonation can be used as a polishing treatment for degrading low-concentration pharmaceutical compounds recalcitrant to biological treatment, when large amounts of biodegradable organics have been previously removed by biological processes. Nevertheless, a systematic investigation has not yet been carried out for the coupled MBR + O3 process through an experimental design approach. Thereby, the purpose of this study is to evaluate the performance of different processes (membrane bioreactor-MBR, ozonation; and integrated MBR + O3) for removing the antibiotic sulfadiazine (SDZ) from a synthetic wastewater matrix of industrial interest. The MBR behavior was monitored over seven months for different parameters (pH, temperature, permeate flow, transmembrane pressure, biological oxygen demand-BOD5, chemical oxygen demand-COD, total organic carbon-TOC, solids, and SDZ concentration). Additionally, the amount of SDZ sorbed onto the sludge was characterized, an issue which is scarcely addressed in most research works. Ozonation experiments were conducted in batch mode in a 2-L glass reactor provided with openings for gas flow. For the MBR + O3 process, the effects of gas flow rate (0.1-1.5 L min-1) and inlet ozone concentration (4-12 mg L-1) on SDZ removal from the MBR permeate were systematically assessed using a Doehlert experimental design and response surface methodology. The results indicated that the MBR system showed good performance regarding organic matter removal efficiency, evaluated in terms of BOD5 (91.5%), COD (93.1%) and TOC (96.3%). In contrast, SDZ was partially removed (33%) by the MBR; in that case, the results indicated that the antibiotic was moderately removed with the sludge and partially biodegraded. In turn, the MBR + O3 system showed excellent performance for removing SDZ (100%), TOC (97%), BOD5 (94%) and COD (97%). The statistical analysis confirmed that the influence of ozone gas flow rate upon the SDZ removal rate was more important than that exhibited by inlet ozone concentration. Therefore, coupling MBR and ozone can be considered a promising alternative for point source treatment of antibiotic production wastewater.

Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design.

Urban-waste bio-organic substances (UW-BOS) have been shown to be capable of extending the photo-Fenton reaction to mildly acidic conditions. In this study, the effects of pH (3-7), UW-BOS, H2O2 and iron concentrations on the photo-Fenton process were systematically assessed using a Doehlert experimental design and response surface methodology for two UW-BOS (CVT230 and FORSUD). Solutions of the model antibiotic sulfadiazine (SDZ) were irradiated in a solar simulator equipped with a 550 W Xenon lamp. The results showed that for UW-BOS contents below 30 mg L-1, SDZ removal proceeds at pH 5 with similar rates for both CVT230 and FORSUD, regardless of Fe(III) concentration. For 50 mg L-1 of UW-BOS or higher, CVT230 performs better than FORSUD, even for low Fe(III) content (1-3 mg L-1). In contrast, half-life times of 35-40 min can only be achieved under mildly acidic conditions with FORSUD for iron concentrations higher than 10 mg L-1. The better performance of CVT230 can be associated with its high hydrophilic/hydrophobic ratio, low E2:E3, higher iron content and possibly higher yields of triplet reactive species generation upon solar irradiation. The most appropriate conditions for each UW-BOS studied are discussed for the first time, which are advantageous for possible engineered applications.

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-).

Photochemical generation of reactive intermediates from urban-waste bio-organic substances under UV and solar irradiation.

Singlet oxygen (1O2), hydroxyl radicals (•OH), and excited triplet states of organic matter (3OM*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of 1O2 and •OH, as well as quantum yield coefficients of TMP degradation (indicative of 3OM* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+1O2) = 8.0 to 8.8 × 10-3, Φ(+•OH) = 4.1 to 4.3 × 10-6, and f TMP = 1.22 to 1.23 × 102 L Einstein-1 under simulated sunlight and from Φ(+1O2) = 1.4 to 2.3 × 10-2, Φ(+•OH) = 1.3 to 3.5 × 10-3, and f TMP = 3.3 to 3.9 × 102 L Einstein-1 under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.

Ultrasonic degradation of sulfadiazine in aqueous solutions.

Advanced oxidation methods, like ultrasound (US), are a promising technology for the degradation of emerging pollutants in water matrices, such as sulfonamide antibiotics. Nevertheless, few authors report the degradation of sulfonamides by high-frequency US (>100 kHz), and limited information exist concerning the use of ultrasonic-driven processes in the case of sulfadiazine (SDZ). In this study, SDZ degradation was investigated with the aim to evaluate the influence of initial concentration, pH and US frequency, and power. Ultrasonic frequencies of 580, 862, and 1,142 kHz at different power values and SDZ initial concentrations of 25, 50, and 70 mg L(-1) were used. The results show that SDZ degradation followed pseudo first-order reaction kinetics with k values and percent removals decreasing for increasing solute initial concentration. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). Addition of the radical scavenger n-butanol confirmed that hydroxyl radical-mediated reactions at the interface of the cavitation bubbles are the prevailing degradation mechanism, which is directly related to the pKa-dependent speciation of SDZ molecules. Finally, addition of H2O2 had a detrimental effect on SDZ degradation, whereas the addition of the Fenton reagent showed a positive effect, revealing to be a promising alternative for the removal of sulfadiazine.