Contaminants of emerging concern: Occurrence, analytical techniques, and removal with electrochemical advanced oxidation processes with special emphasis in Latin America.

The occurrence of contaminants of emerging concern (CECs) in environmental systems is gradually more studied worldwide. However, in Latin America, the presence of contaminants of emerging concern, together with their environmental and toxicological impacts, has recently been gaining wide interest in the scientific community. This paper presents a critical review about the source, fate, and occurrence of distinct emerging contaminants reported during the last two decades in various countries of Latin America. In recent years, Brazil, Chile, and Colombia are the main countries that have conducted research on the presence of these pollutants in biological and aquatic compartments. Data gathered indicated that pharmaceuticals, pesticides, and personal care products are the most assessed CECs in Latin America, being the most common compounds the followings: atrazine, acenaphthene, caffeine, carbamazepine, ciprofloxacin, diclofenac, diuron, estrone, losartan, sulfamethoxazole, and trimethoprim. Most common analytical methodologies for identifying these compounds were HPLC and GC coupled with mass spectrometry with the potential to characterize and quantify complex substances in the environment at low concentrations. Most CECs' monitoring and detection were observed near to urban areas which confirm the out-of-date wastewater treatment plants and sanitization infrastructures limiting the removal of these pollutants. Therefore, the implementation of tertiary treatment should be required. In this tenor, this review also summarizes some studies of CECs removal using electrochemical advanced oxidation processes that showed satisfactory performance. Finally, challenges, recommendations, and future perspectives are discussed.

Degradation of contaminants of emerging concern in a secondary effluent using synthesized MOF-derived photoanodes: A comparative study between photo-, electro- and photoelectrocatalysis.

Three metal-organic framework (MOF)-based photoanodes were prepared by deposition on TiO2 nanotubes using Ti as substrate (Ti/TiO2NT): i) Ti/TiO2NT-Au@ZIF-8, ii) Ti/TiO2NT-Ru3(BTC)2, iii) Ti/TiO2NT-UiO-66(Zr)NH2. These photoanodes were characterized by FEG-SEM, EDX and DRX. The analyses showed a successful modification and a high homogeneity of the different MOFs on the Ti/TiO2NT surface. The photoanodes were studied in the degradation of Contaminants of Emerging Concern (CECs) in a spiked secondary effluent from a Municipal Wastewater Treatment Plant (MWWTP). Sodium diclofenac (DCF), sulfamethazine (SMT) and carbamazepine (CBZ) were used as CECs at low concentration (200 µg/L each CEC). The samples were preconcentrated using Solid Phase Extraction (SPE) and analyzed by a HPLC-DAD system. The MOF-based photoanodes exhibited a high photoelectrochemical (PEC) activity towards the oxidation of CECs, achieving up to 50%, 70% and 80% of removal using Ti/TiO2NT-Au@ZIF-8, Ti/TiO2NT-UiO-66(Zr)NH2, Ti/TiO2NT-Ru3(BTC), respectively. The influence of the generation of hydroxyl radical was then studied. The results indicate that PEC degradation using Ti/TiO2NT-Ru3(BTC)2 and Ti/TiO2NT-UiO-66(Zr)NH2 is more affected by the concentration of the radical.

New development of a solar electrochemical raceway pond reactor for industrial wastewater treatment.

In this work, a solar electrochemical-raceway pond reactor (SEC-RPR) is used to treat textile industrial wastewater by solar photoelectron-Fenton (SPEF) at pilot plant scale for the first time. The SEC-RPR is composed of an electrochemical filter press-cell coupled to RPR, where H2O2 is electro-generated. A complete study about experimental variables such as current, catalyst concentration, pollutant load or liquid depth is conducted based on methyl orange removal, mineralization and decolorization. Validation of the SPEF process using SEC-RPR reached more than 80% of mineralization, as well as the complete decolorization of the solution. The good performance of the SPEF treatment in the new SEC-RPR led to quick degradation kinetics, mainly due to the synergetic action of solar radiation and good distribution of H2O2 electrogenerated in the photoreactor. 100% Methyl Orange degradation was achieved after 150, 60, 45, 30 and 20 min of reaction time applying current density equal to 5, 10, 20, 40 and 60 mA cm-2, respectively. However, the increase of current density decreased the mineralization current efficiency. Up to 10 aromatics intermediates and 5 short-chain carboxylic acids were identified by LC-MS and HPLC analysis and a reaction pathway for MO mineralization by SPEF is proposed. This study represents an essential preliminary step towards the development of the first SEC-RPR at demo scale.

Simultaneous degradation of 30 pharmaceuticals by anodic oxidation: Main intermediaries and by-products.

The anodic oxidation (AO) of 30 pharmaceuticals including antibiotics, hormones, antihistaminics, anti-inflammatories, antidepressants, antihypertensives, and antiulcer agents, in solutions containing different supporting electrolytes media (0.05 M Na2SO4, 0.05 M NaCl, and 0.05 M Na2SO4 + 0.05 M NaCl) at natural pH was studied. A boron-doped diamond (BDD) electrode and a stainless-steel electrode were used as anode and cathode, respectively, and three current densities of 6, 20, and 40 mA cm-2 were applied. The results showed high mineralization rates, above 85%, in all the tested electrolytic media. 25 intermediaries produced during the electrooxidation were identified, depending on the supporting electrolyte together with the formation of carboxylic acids, NO3-, SO42- and NH4+ ions. The formation of intermediates in chloride medium produced an increase in absorbance. Finally, a real secondary effluent spiked with the 30 pharmaceuticals was treated by AO applying 6 mA cm-2 at natural pH and without addition of supporting electrolyte, reaching c.a. 90% mineralization after 300 min, with an energy consumption of 18.95 kW h m-3 equivalent to 2.90 USD m-3. A degradation scheme for the mixture of emerging contaminants in both electrolytic media is proposed. Thus, the application of anodic oxidation generates a high concentration of hydroxyl radicals that favors the mineralization of the pharmaceuticals present in the spiked secondary effluent sample.